Detergent compositions

ABSTRACT

The present invention relates to detergent compositions containing at least one anionic surfactant, one or more cationic surfactants of the formula: R 1  R 2  R 3  R 4  N+X -   in which R 1  is an optionally substituted phenol or hydroxyalkyl group having no greater than 6 carbon atoms; each of R 2  and R 3  is independently selected from C 1-4  alkyl or alkenyl; R 4  is a C[ 6  ] 5-11  alkyl or alkenyl; X -   is a counterion, and a cationic dye-fixing agent.

TECHNICAL FIELD

The present invention relates to detergent compositions or componentsthereof containing cationic surfactant and a dye-fixing agent. Generallythe detergent compositions of the invention are for use in laundrywashing processes.

BACKGROUND TO THE INVENTION

It is known to use cationic surfactants in detergent compositions. Forexample, GB 2040990A describes granular detergent compositionscomprising cationic surfactants.

It is also known to incorporate cationic polyamine dye-fixing agentsinto detergent compositions, as described in EP-A-462806.

However, formulations containing such polyamines exhibit poor stainremoval properties as they tend to coat fabric surfaces thus trappingany stains on the fabric surface. Use of anionic surfactants to solvethis problem may promote dye fading. The Applicants have found that thisproblem can be alleviated by the use of a cationic surfactant incombination with the cationic polyamine dye-fixing agents.

Furthermore, it is believed that following breakdown of an oily soil bythe enzyme, the cationic surfactants used in the present invention mayform complexes with the fatty acids and any other negatively chargedbreakdown product produced, increasing their solubility and enhancinggreasy, oily soil removal and overall cleaning performance, prior todeposition of the dye-fixing agents.

All documents cited in the present description are incorporated hereinby reference.

SUMMARY OF THE INVENTION

The present invention relates to a detergent composition or componentthereof which comprises

(a) a cationic dye-fixing agent; and

(b) a cationic surfactant of formula I:

    R.sup.1 R.sup.2 R.sup.3 R.sup.4 N.sup.+ X.sup.-            (I)

in which R¹ is a hydroxyalkyl group having no greater than 6 carbonatoms; each of R² and R³ is independently selected from C₁₋₄ alkyl oralkenyl; R⁴ is a C₅₋₁₈ alkyl or alkenyl; and X⁻ is a counterion.

Unless otherwise stated alkyl or alkenyl as used herein may be branched,linear or substituted. Substituents may be for example, aromatic groups,heterocyclic groups containing one or more N, S or O atoms, or halosubstituents.

DETAILED DESCRIPTION OF THE INVENTION

Cationic Surfactant

The cationic surfactant is generally present in the composition orcomponent thereof in an amount no greater than 60% by weight, preferablyno greater than 10% by weight, most preferably in an amount no greaterthan 4.5% or even 3% by weight. The benefits of the invention are foundeven with very small amounts of the cationic surfactant of formula I.Generally there will be at least 0.01% by weight, preferably at least0.05% or at least 0.1% by weight of the cationic surfactant in thedetergent compositions of the invention.

Preferably R¹ in formula I is a hydroxyalkyl group, having no greaterthan 6 carbon atoms and preferably the --OH group is separated from thequaternary ammonium nitrogen atom by no more than 3 carbon atoms.Preferred R¹ groups are --CH₂ CH₂ OH, --CH₂ CH₂ CH₂ OH, --CH₂ CH(CH₃)OHand --CH(CH₃)CH₂ OH. --CH₂ CH₂ OH and --CH₂ CH₂ CH₂ OH are mostpreferred and --CH₂ CH₂ OH is particularly preferred. Preferably R² andR³ are each selected from ethyl and methyl groups and most preferablyboth R² and R³ are methyl groups. Preferred R⁴ groups have at least 6 oreven at least 7 carbon atoms. R⁴ may have no greater than 9 carbonatoms, or even no greater than 8 or 7 carbon atoms. Preferred R⁴ groupsare linear alkyl groups. Linear R⁴ groups having from 8 to 11 carbonatoms, or from 8 to 10 carbon atoms are preferred. Preferably each of R²and R³ is selected from C₁₋₄ alkyl and R⁴ is C₆₋₁₁ alkyl or alkenyl.

Whilst pure or substantially pure cationic compounds are within theambit of this invention, it has been found that mixtures of the cationicsurfactants of formula I may be particularly effective, for example,surfactant mixtures in which R⁴ may be a combination of C₈ and C₁₀linear alkyl groups, or C₉ and C₁₁ alkyl groups. According to one aspectof the invention a mixture of cationic surfactants of formula I ispresent in the composition, the mixture comprising from a shorter alkylchain surfactant of formula I and a longer alkyl chain surfactant offormula I. The longer alkyl chain cationic surfactant is preferablyselected from the surfactants of formula I where R⁴ is an alkyl grouphaving n carbon atoms where n is from 8 to 11; the shorter alkyl chainsurfactant is preferably selected from those of formula I where R⁴ is analkyl group having (n-2) carbon atoms. Such cationic surfactant mixturesgenerally comprise 5 to 95% by weight total cationic surfactant offormula I of a longer alkyl chain length, preferably from 30 to 90% andmost preferably at least 50% by weight of the mixture. Generally themixtures will contain from 5 to 95% by weight, preferably from 5 to 70%,more preferably 35 to 65% by weight and most preferably at least 40% byweight of shorter alkyl chain cationic surfactant of formula I.

The invention also comprises a detergent composition comprising cationicdye-fixing agent; and a mixture of cationic surfactants of formula Iwherein in the mixture of cationic surfactants of formula I, at least10% by weight preferably at least 20% by weight have R⁴ which is C₅₋₉alkyl or alkenyl.

X in formula I may be any counterion providing electrical neutrality,but is preferably selected from the group consisting of halide, methylsulfate, sulfate and nitrate, more preferably being selected from methylsulfate, chloride, bromide and iodide. The halide ions, especiallychloride are most preferred.

Cationic Dye-Fixing Agent

Dye fixing agents suitable for use in the present invention are ammoniumcompounds such as fatty acid--diamine condensates e.g. thehydrochloride, acetate, methosulphate and benzyl hydrochloride ofoleyldiethyl aminoethylamide, oleylmethyl-diethylenediaminemethsulphate,monostearyl-ethylene diaminotrimethylammonium methosulfate and oxidisedproducts of tertiary amines; derivatives of polymeric alkyldiamines,polyamine-cyanuric chloride condensates and aminated glyceroldichlorohydrine as described in EP-A-0462806.

Particularly preferred dye fixing agents suitable for use in the processof the invention are cationic species and examples include aliphaticpolyamines such as Indosol E-50 (Sandoz) and Croscolor NOFF adimethyldiallyl ammonium chloride polymer of molecular weight in therange 2,000 to 20,000 (Crosfield). Other cationic dye fixing agents aredescribed in "After-treatments for Improving the Fastness of Dyes onTextile Fibres" by Christopher C. Cook (Rev. Prog. Coloration Vol 121982).

The amount of dye-fixing agent in the detergent compositions of theinvention is generally from 0.01 to 50% by weight, preferably from 0.5to 30% by weight and most preferably from 1 to 20% by weight. The weightratio of cationic dye-fixing agent to cationic surfactant is generallyfrom 50:1 to 1:10, more preferably from 20:1 to 1:2, most preferablyfrom 10:1 to 3:2.

Additional Detergent Components

The detergent compositions or components thereof in accordance with thepresent invention may also contain additional detergent components. Theprecise nature of these additional components, and levels ofincorporation thereof will depend on the physical form of thecomposition or component thereof, and the precise nature of the washingoperation for which it is to be used.

The compositions or components thereof, of the invention preferablycontain one or more additional detergent components selected fromadditional surfactants, builders, sequestrants, fabric softeningcompounds, bleach, bleach precursors, bleach catalysts, organicpolymeric compounds, additional enzymes, suds suppressors, lime soapdispersants, additional soil suspension and anti-redeposition agentssoil releasing agents, perfumes and corrosion inhibitors.

Additional Surfactant

The detergent compositions or components thereof in accordance with theinvention preferably contain an additional surfactant selected fromanionic, nonionic, cationic, ampholytic, amphoteric and zwitterionicsurfactants and mixtures thereof.

A typical listing of anionic, nonionic, ampholytic, and zwitterionicclasses, and species of these surfactants, is given in U.S. Pat. No.3,929,678 issued to Laughlin and Heuring on Dec. 30, 1975. Furtherexamples are given in "Surface Active Agents and Detergents" (Vol. I andII by Schwartz, Perry and Berch). A list of suitable cationicsurfactants is given in U.S. Pat. No. 4,259,217 issued to Murphy on Mar.31, 1981.

Where present, ampholytic, amphoteric and zwitteronic surfactants aregenerally used in combination with one or more anionic and/or nonionicsurfactants.

Anionic Surfactant

The detergent compositions of the invention may additionally comprise ananionic surfactant. Any anionic surfactant useful for detersive purposesis suitable. These can include salts (including, for example, sodium,potassium, ammonium, and substituted ammonium salts such as mono-, di-and triethanolamine salts) of the anionic sulfate, sulfonate,carboxylate and sarcosinate surfactants. Anionic sulfate surfactants arepreferred.

Other suitable anionic surfactants include the isethionates such as theacyl isethionates, N-acyl taurates, fatty acid amides of methyl tauride,alkyl succinates and sulfosuccinates, monoesters of sulfosuccinate(especially saturated and unsaturated C₁₂ -C₁₈ monoesters) diesters ofsulfosuccinate (especially saturated and unsaturated C₆ -C₁₄ diesters),N-acyl sarcosinates. Resin acids and hydrogenated resin acids are alsosuitable, such as rosin, hydrogenated rosin, and resin acids andhydrogenated resin acids present in or derived from tallow oil.

Anionic Sulfate Surfactant

Anionic sulfate surfactants suitable for use in the compositions of theinvention include the linear and branched primary and secondary alkylsulfates, alkyl ethoxysulfates, fatty oleoyl glycerol sulfates, alkylphenol ethylene oxide ether sulfates, the C₅ -C₁₇ acyl-N-(C₁ -C₄ alkyl)and --N--(C₁ -C₂ hydroxyalkyl) glucamine sulfates, and sulfates ofalkylpolysaccharides such as the sulfates of alkylpolyglucoside (thenonionic nonsulfated compounds being described herein).

Alkyl ethoxysulfate surfactants are preferably selected from the groupconsisting of the C₉ -C₂₂ alkyl sulfates which have been ethoxylatedwith from 0.5 to 20 moles of ethylene oxide per molecule. Morepreferably, the alkyl ethoxysulfate surfactant is a C₁₁ -C₁₈, mostpreferably C₁₁ -C₁₅ alkyl sulfate which has been ethoxylated with from0.5 to 7, preferably from 1 to 5, moles of ethylene oxide per molecule.

A particularly preferred aspect of the invention employs mixtures of thepreferred alkyl sulfate and alkyl ethoxysulfate surfactants. Suchmixtures have been disclosed in PCT Patent Application No. WO 93/18124.

Anionic Sulfonate Surfactant

Anionic sulfonate surfactants suitable for use herein include the saltsof C₅ -C₂₀ linear alkylbenzene sulfonates, alkyl ester sulfonates, C₆-C₂₂ primary or secondary alkane sulfonates, C₆ -C₂₄ olefin sulfonates,sulfonated polycarboxylic acids, alkyl glycerol sulfonates, fatty acylglycerol sulfonates, fatty oleyl glycerol sulfonates, and any mixturesthereof.

Particularly preferred compositions of the present inventionadditionally comprise an anionic surfactant, selected from alkyl sulfateand/or alkylbenzene sulphonate surfactants of formula II and III,respectively:

    R.sup.5 OSO.sub.3.sup.- M.sup.+                            (II)

    R.sup.6 SO.sub.3.sup.- M'.sup.+                            (III)

wherein R⁵ is a linear or branched alkyl or alkenyl moiety having from 9to 22 carbon atoms, preferably C₁₂ to C₁₈ alkyl or as found in secondaryalkyl sulfates; R⁶ is C₁₀ -C₁₆ alkylbenzene, preferably C₁₁ -C₁₃alkylbenzene; M⁺ and M'⁺ can vary independently and are selected fromalkali metals, alkaline earths, alkanolammonium and ammonium.

Particularly preferred compositions of the invention comprise both analkyl sulfate surfactant and an alkyl benzene surfactant, preferably inratios of II to III of from 15:1 to 1:2, most preferably from 12:1 to2:1.

Amounts of the one or mixtures of more than one anionic surfactant inthe preferred composition may be from 1% to 50%, however, preferablyanionic surfactant is present in amounts of from 5% to 40% by weight ofthe composition. Preferred amounts of the alkyl sulfate surfactant offormula II are from 3% to 40%, or more preferably 6% to 30% by weight ofthe detergent composition. Preferred amounts of the alkyl benzenesulphonate surfactant of formula III in the detergent composition arefrom at least 1%, preferably at least 2%, or even at least 4% by weight.Preferred amounts of the alkyl benzene sulphonate surfactant are up to23%, more preferably no greater than 20%, most preferably up to 15% oreven 10%.

The performance benefits which result when an anionic surfactant is alsoused in the compositions of the invention are particularly useful forlonger carbon chain length anionic surfactants such as those having acarbon chain length of C₁₂ or greater, particularly of C_(14/15) or evenup to C₁₆₋₁₈ carbon chain lengths.

In preferred embodiments of the detergent compositions of the inventioncomprising anionic surfactant there will be a significant excess ofanionic surfactants, preferably a weight ratio of anionic to cationicsurfactant of from 50:1 to 2:1, most preferably 30:1 to 8:1. However,the benefits of the invention are also achieved where the ratio ofcationic surfactant to anionic surfactant is substantiallystoichiometric, for example from 3:2 to 4:3.

In a preferred embodiment of the invention the essential cationicsurfactant of formula I is intimately mixed with one or more anionicsurfactants prior to addition of the other detergent compositioncomponents.

Anionic Carboxylate Surfactant

Suitable anionic carboxylate surfactants include the alkyl ethoxycarboxylates, the alkyl polyethoxy polycarboxylate surfactants and thesoaps (`alkyl carboxyls`), especially certain secondary soaps asdescribed herein.

Suitable alkyl ethoxy carboxylates include those with the formula RO(CH₂CH₂ O).sub.× CH₂ COO⁻ M⁺ wherein R is a C₆ to C₁₈ alkyl group, x rangesfrom 0 to 10, and the ethoxylate distribution is such that, on a weightbasis, the amount of material where x is 0 is less than 20% and M is acation. Suitable alkyl polyethoxy polycarboxylate surfactants includethose having the formula RO--(CHR₁ --CHR₂ --O)--R₃ wherein R is a C₆ toC₁₈ alkyl group, x is from 1 to 25, R₁ and R₂ are selected from thegroup consisting of hydrogen, methyl acid radical, succinic acidradical, hydroxysuccinic acid radical, and mixtures thereof, and R₃ isselected from the group consisting of hydrogen, substituted orunsubstituted hydrocarbon having between 1 and 8 carbon atoms, andmixtures thereof.

Suitable soap surfactants include the secondary soap surfactants whichcontain a carboxyl unit connected to a secondary carbon. Preferredsecondary soap surfactants for use herein are water-soluble membersselected from the group consisting of the water-soluble salts of2-methyl-1-undecanoic acid, 2-ethyl-1-decanoic acid, 2-propyl-1-nonanoicacid, 2-butyl-1-octanoic acid and 2-pentyl-1-heptanoic acid. Certainsoaps may also be included as suds suppressors.

Alkali Metal Sarcosinate Surfactant

Other suitable anionic surfactants are the alkali metal sarcosinates offormula R--CON (R¹) CH₂ COOM, wherein R is a C₅ -C₁₇ linear or branchedalkyl or alkenyl group, R¹ is a C₁ -C₄ alkyl group and M is an alkalimetal ion. Preferred examples are the myristyl and oleoyl methylsarcosinates in the form of their sodium salts.

Alkoxylated Nonionic Surfactant

Essentially any alkoxylated nonionic surfactants are suitable herein.The ethoxylated and propoxylated nonionic surfactants are preferred.Linear or branched alkoxylated groups are suitable.

Preferred alkoxylated surfactants can be selected from the classes ofthe nonionic condensates of alkyl phenols, nonionic ethoxylatedalcohols, nonionic ethoxylated/propoxylated fatty alcohols, nonionicethoxylate/propoxylate condensates with propylene glycol, and thenonionic ethoxylate condensation products with propylene oxide/ethylenediamine adducts.

Nonionic Alkoxylated Alcohol Surfactant

The condensation products of aliphatic alcohols with from 1 to 25 molesof alkylene oxide, particularly ethylene oxide and/or propylene oxide,are suitable for use herein. The alkyl chain of the aliphatic alcoholcan either be straight or branched, primary or secondary, and generallycontains from 6 to 22 carbon atoms. Particularly preferred are thecondensation products of alcohols having an alkyl group containing from8 to 20 carbon atoms with from 2 to 10 moles of ethylene oxide per moleof alcohol.

Nonionic Polyhydroxy Fatty Acid Amide Surfactant

Polyhydroxy fatty acid amides suitable for use herein are those havingthe structural formula R² CONR¹ Z wherein: R1 is H, C₁ -C₄ hydrocarbyl,2-hydroxy ethyl, 2-hydroxy propyl, ethoxy, propoxy, or a mixturethereof, preferable C1-C4 alkyl, more preferably C₁ or C₂ alkyl, mostpreferably C₁ alkyl (i.e., methyl); and R₂ is a C₅ -C₃₁ hydrocarbyl,preferably straight-chain C₅ -C₁₉ alkyl or alkenyl, more preferablystraight-chain C₉ -C₁₇ alkyl or alkenyl, most preferably straight-chainC₁₁ -C₁₇ alkyl or alkenyl, or mixture thereof; and Z is apolyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3hydroxyls directly connected to the chain, or an alkoxylated derivative(preferably ethoxylated or propoxylated) thereof. Z preferably will bederived from a reducing sugar in a reductive amination reaction; morepreferably Z is a glycityl.

Nonionic Fatty Acid Amide Surfactant

Suitable fatty acid amide surfactants include those having the formula:R⁶ CON(R⁷)₂ wherein R⁶ is an alkyl group containing from 7 to 21,preferably from 9 to 17 carbon atoms and each R⁷ is selected from thegroup consisting of hydrogen, C₁ -C₄ alkyl, C₁ -C₄ hydroxyalkyl, and--(C₂ H₄ O)_(x) H, where x is in the range of from 1 to 3.

Nonionic Alkylpolysaccharide Surfactant

Suitable alkylpolysaccharides for use herein are disclosed in U.S. Pat.No. 4,565,647, Llenado, issued Jan. 21, 1986, having a hydrophobic groupcontaining from 6 to 30 carbon atoms and a polysaccharide, e.g., apolyglycoside, hydrophilic group containing from 1.3 to 10 saccharideunits.

Preferred alkylpolyglycosides have the formula

    R.sup.2 O(C.sub.n H.sub.2n O)t(glycosyl).sub.x

wherein R² is selected from the group consisting of alkyl, alkylphenyl,hydroxyalkyl, hydroxyalkylphenyl, and mixtures thereof in which thealkyl groups contain from 10 to 18 carbon atoms; n is 2 or 3; t is from0 to 10, and x is from 1.3 to 8. The glycosyl is preferably derived fromglucose.

Amphoteric Surfactant

Suitable amphoteric surfactants for use herein include the amine oxidesurfactants and the alkyl amphocarboxylic acids.

Suitable amine oxides include those compounds having the formula R³(OR⁴)_(x) N⁰ (R⁵)₂ wherein R³ is selected from an alkyl, hydroxyalkyl,acylamidopropoyl and alkyl phenyl group, or mixtures thereof, containingfrom 8 to 26 carbon atoms; R⁴ is an alkylene or hydroxyalkylene groupcontaining from 2 to 3 carbon atoms, or mixtures thereof; x is from 0 to5, preferably from 0 to 3; and each R⁵ is an alkyl or hydroxyalkyl groupcontaining from 1 to 3, or a polyethylene oxide group containing from 1to 3 ethylene oxide groups. Preferred are C₁₀ -C₁₈ alkyl dimethylamineoxide, and C₁₀₋₁₈ acylamido alkyl dimethylamine oxide.

A suitable example of an alkyl aphodicarboxylic acid is Miranol(TM) C2MConc. manufactured by Miranol, Inc., Dayton, N.J.

Zwitterionic Surfactant

Zwitterionic surfactants can also be incorporated into the detergentcompositions or components thereof in accord with the invention. Thesesurfactants can be broadly described as derivatives of secondary andtertiary amines, derivatives of heterocyclic secondary and tertiaryamines, or derivatives of quaternary ammonium, quaternary phosphonium ortertiary sulfonium compounds. Betaine and sultaine surfactants areexemplary zwitterionic surfactants for use herein.

Suitable betaines are those compounds having the formula R(R')₂ N⁺ R²COO⁻ wherein R is a C₆ -C₁₈ hydrocarbyl group, each R¹ is typically C₁-C₃ alkyl, and R² is a C₁ -C₅ hydrocarbyl group. Preferred betaines areC₁₂₋₁₈ dimethyl-ammonio hexanoate and the C₁₀₋₁₈ acylamidopropane (orethane) dimethyl (or diethyl) betaines. Complex betaine surfactants arealso suitable for use herein.

Additional Cationic Surfactants

The compositions of the invention are preferably substantially free ofquaternary ammonium compounds of formula I but wherein one or R¹, R², R³or R⁴ is an alkyl chain group longer than C₁₁. Preferably thecomposition should contain less than 1%, preferably less than 0.1% byweight or even less than 0.05% and most preferably less than 0.01% byweight of compounds of formula I having a linear (or even branched)alkyl group having 12 or more carbon atoms.

Another suitable group of cationic surfactants which can be used in thedetergent compositions of the invention are cationic ester surfactants.The cationic ester surfactant is a compound having surfactant propertiescomprising at least one ester (i.e. --COO--) linkage and at least onecationically charged group. Preferred cationic ester surfactants arewater dispersible.

Suitable cationic ester surfactants, including choline estersurfactants, have for example been disclosed in U.S. Pat. Nos.4,228,042, 4,239,660 and 4,260,529.

In preferred cationic ester surfactants the ester linkage andcationically charged group are separated from each other in thesurfactant molecule by a spacer group consisting of a chain comprisingat least three atoms (i.e. of three atoms chain length), preferably fromthree to eight atoms, more preferably from three to five atoms, mostpreferably three atoms. The atoms forming the spacer group chain areselected from the group consisting of carbon, nitrogen and oxygen atomsand any mixtures thereof, with the proviso that any nitrogen or oxygenatom in said chain connects only with carbon atoms in the chain. Thusspacer groups having, for example, --O--O-- (i.e. peroxide), --N--N--,and --N--O-- linkages are excluded, whilst spacer groups having, forexample --CH₂ --O-- CH₂ -- and --CH₂ --NH--CH₂ -- linkages are included.In a preferred aspect the spacer group chain comprises only carbonatoms, most preferably the chain is a hydrocarbyl chain.

Fabric Softening Compounds

Compounds having fabric softening properties are preferred additionaldetergent components.

Suitable fabric softening compounds include cationic fabric softeningmaterials and nonionic fabric softening materials. Suitable materialsinclude substantially water-insoluble quaternary ammonium compounds asdescribed in EP 89200545.5 and EP 239910; amine materials; amphotericfabric conditioning materials as described in EP 89200545.5, clays,polysiloxanes as disclosed in EP-A-150867 (Procter & Gamble Co.); andnonionic cellulose ethers as disclosed in EP-A-213730 (Unilever).

Alkalinity

In the detergent compositions of the present invention preferably analkalinity system is present to achieve optimal cationic surfactantperformance. The alkalinity system comprises components capable ofproviding alkalinity species in solution. Examples of alkalinity speciesinclude carbonate, bicarbonate, hydroxide, the various silicate anions,percarbonate, perborates, perphosphates, persulfate and persilicate.Such alkalinity species can be formed for example, when alkaline saltsselected from alkali metal or alkaline earth carbonate, bicarbonate,hydroxide or silicate, including crystalline layered silicate, salts andpercarbonate, perborates, perphosphates, persulfate and persilicatesalts and any mixtures thereof are dissolved in water.

Examples of carbonates are the alkaline earth and alkali metalcarbonates, including sodium carbonate and sesqui-carbonate and anymixtures thereof with ultra-fine calcium carbonate such as are disclosedin German Patent Application No. 2,321,001 published on Nov. 15, 1973.

Suitable silicates include the water soluble sodium silicates with anSiO₂ :NA₂ O ratio of from 1.0 to 2.8, with ratios of from 1.6 to 2.0being preferred, and 2.0 ratio being most preferred. The silicates maybe in the form of either the anhydrous salt or a hydrated salt. Sodiumsilicate with an SiO₂ :Na₂ O ratio of 2.0 is the most preferredsilicate.

Preferred crystalline layered silicates for use herein have the generalformula

    NaMSi.sub.x O.sub.2x+1.yH.sub.2 O

wherein M is sodium or hydrogen, x is a number from 1.9 to 4 and y is anumber from 0 to 20. Crystalline layered sodium silicates of this typeare disclosed in EP-A-0164514 and methods for their preparation aredisclosed in DE-A-3417649 and DE-A-3742043. Herein, x in the generalformula above preferably has a value of 2, 3 or 4 and is preferably 2.The most preferred material is δ-Na₂ Si₂ O₅, available from Hoechst AGas NaSKS-6.

Water-soluble Builder Compound

The detergent compositions in accordance with the present inventionpreferably contain a water-soluble builder compound, typically presentin detergent compositions at a level of from 1% to 80% by weight,preferably from 10% to 70% by weight, most preferably from 20% to 60% byweight of the composition.

Suitable water-soluble builder compounds include the water solublemonomeric polycarboxylates, or their acid forms, homo or copolymericpolycarboxylic acids or their salts in which the polycarboxylic acidcomprises at least two carboxylic radicals separated from each other bynot more that two carbon atoms, borates, phosphates, and mixtures of anyof the foregoing.

The carboxylate or polycarboxylate builder can be monomeric oroligomeric in type although monomeric polycarboxylates are generallypreferred for reasons of cost and performance.

Suitable carboxylates containing one carboxy group include the watersoluble salts of lactic acid, glycolic acid and ether derivativesthereof. Polycarboxylates containing two carboxy groups include thewater-soluble salts of succinic acid, malonic acid, (ethylenedioxy)diacetic acid, maleic acid, diglycolic acid, tartaric acid, tartronicacid and fumaric acid, as well as the ether carboxylates and thesulfinyl carboxylates. Polycarboxylates containing three carboxy groupsinclude, in particular, water-soluble citrates, aconitrates andcitraconates as well as succinate derivatives such as thecarboxymethyloxysuccinates described in British Patent No. 1,379,241,lactoxysuccinates described in British Patent No. 1,389,732, andaminosuccinates described in Netherlands Application 7205873, and theoxypolycarboxylate materials such as 2-oxa-1,1,3-propane tricarboxylatesdescribed in British Patent No. 1,387,447.

Polycarboxylates containing four carboxy groups include oxydisuccinatesdisclosed in British Patent No. 1,261,829, 1,1,2,2-ethanetetracarboxylates, 1,1,3,3-propane tetracarboxylates and 1,1,2,3-propanetetracarboxylates. Polycarboxylates containing sulfo substituentsinclude the sulfosuccinate derivatives disclosed in British Patent Nos.1,398,421 and 1,398,422 and in U.S. Pat. No. 3,936,448, and thesulfonated pyrolysed citrates described in British Patent No. 1,439,000.Preferred polycarboxylates are hydroxycarboxylates containing up tothree carboxy groups per molecule, more particularly citrates.

The parent acids of the monomeric or oligomeric polycarboxylatechelating agents or mixtures thereof with their salts, e.g. citric acidor citrate/citric acid mixtures are also contemplated as useful buildercomponents.

Borate builders, as well as builders containing borate-forming materialsthat can produce borate under detergent storage or wash conditions areuseful water-soluble builders herein.

Suitable examples of water-soluble phosphate builders are the alkalimetal tripolyphosphates, sodium, potassium and ammonium pyrophosphate,sodium and potassium and ammonium pyrophosphate, sodium and potassiumorthophosphate, sodium polymeta/phosphate in which the degree ofpolymerization ranges from about 6 to 21, and salts of phytic acid.

Partially Soluble or Insoluble Builder Compound

The detergent compositions or components thereof, of the presentinvention may contain a partially soluble or insoluble builder compound,typically present in detergent compositions at a level of from 1% to 80%by weight, preferably from 10% to 70% by weight, most preferably from20% to 60% weight of the composition.

Examples of largely water insoluble builders include the sodiumaluminosilicates.

Suitable aluminosilicate zeolites have the unit cell formula Na_(z)[(AlO₂)_(z) (SiO₂)y].xH₂ O wherein z and y are at least 6; the molarratio of z to y is from 1.0 to 0.5 and x is at least 5, preferably from7.5 to 276, more preferably from 10 to 264. The aluminosilicatematerials are in hydrated form and are preferably crystalline,containing from 10% to 28%, more preferably from 18% to 22% water inbound form.

The aluminosilicate zeolites can be naturally occurring materials, butare preferably synthetically derived. Synthetic crystallinealuminosilicate ion exchange materials are available under thedesignations Zeolite A, Zeolite B, Zeolite P, Zeolite X, Zeolite HS andmixtures thereof. Zeolite A has the formula

    Na.sub.12 [(AlO.sub.2).sub.12 (SiO.sub.2).sub.12 ]. xH.sub.2 O

wherein x is from 20 to 30, especially 27. Zeolite X has the formulaNa₈₆ [(AlO₂)₈₆ (SiO₂)₁₀₆ ]. 276 H₂ O.

Another preferred aluminosilicate zeolite is zeolite MAP builder. Thezeolite MAP can be present at a level of from 1% to 80%, more preferablyfrom 15% to 40% by weight of the compositions.

Zeolite MAP is described in EP 384070A (Unilever). It is defined as analkali metal alumino-silicate of the zeolite P type having a silicon toaluminium ratio not greater than 1.33, preferably within the range from0.9 to 1.33 and more preferably within the range of from 0.9 to 1.2.

Of particular interest is zeolite MAP having a silicon to aluminiumratio not greater than 1.15 and, more particularly, not greater than1.07.

In a preferred aspect the zeolite MAP detergent builder has a particlesize, expressed as a d₅₀ value of from 1.0 to 10.0 micrometres, morepreferably from 2.0 to 7.0 micrometres, most preferably from 2.5 to 5.0micrometres.

The d₅₀ value indicates that 50% by weight of the particles have adiameter smaller than that figure. The particle size may, in particularbe determined by conventional analytical techniques such as microscopicdetermination using a scanning electron microscope or by means of alaser granulometer. Other methods of establishing d₅₀ values aredisclosed in EP 384070A.

Heavy Metal Ion Seguestrant

The detergent compositions or components thereof in accordance with thepresent invention preferably contain as an optional component a heavymetal ion sequestrant. By heavy metal ion sequestrant it is meant hereincomponents which act to sequester (chelate) heavy metal ions. Thesecomponents may also have calcium and magnesium chelation capacity, butpreferentially they show selectivity to binding heavy metal ions such asiron, manganese and copper.

Heavy metal ion sequestrants are generally present at a level of from0.005% to 20%, preferably from 0.1% to 10%, more preferably from 0.25%to 7.5% and most preferably from 0.5% to 5% by weight of thecompositions.

Suitable heavy metal ion sequestrants for use herein include organicphosphonates, such as the amino alkylene poly (alkylene phosphonates),alkali metal ethane 1-hydroxy disphosphonates and nitrilo trimethylenephosphonates.

Preferred among the above species are diethylene triamine penta(methylene phosphonate), ethylene diamine tri (methylene phosphonate)hexamethylene diamine tetra (methylene phosphonate) and hydroxy-ethylene1,1 diphosphonate.

Other suitable heavy metal ion sequestrant for use herein includenitrilotriacetic acid and polyaminocarboxylic acids such asethylenediaminotetracetic acid, ethylenetriamine pentacetic acid,ethylenediamine disuccinic acid, ethylenediamine diglutaric acid,2-hydroxypropylenediamine disuccinic acid or any salts thereof.Especially preferred is ethylenediamine-N,N'-disuccinic acid (EDDS) orthe alkali metal, alkaline earth metal, ammonium, or substitutedammonium salts thereof, or mixtures thereof.

Other suitable heavy metal ion sequestrants for use herein areiminodiacetic acid derivatives such as 2-hydroxyethyl diacetic acid orglyceryl imino diacetic acid, described in EP-A-317,542 andEP-A-399,133. The iminodiacetic acid-N-2-hydroxypropyl sulfonic acid andaspartic acid N-carboxymethyl N-2-hydroxypropyl-3-sulfonic acidsequestrants described in EP-A-516,102 are also suitable herein. Theβ-alanine-N,N'-diacetic acid, aspartic acid-N,N'-diacetic acid, asparticacid-N-monoacetic acid and iminodisuccinic acid sequestrants describedin EP-A-509,382 are also suitable.

EP-A-476,257 describes suitable amino based sequestrants. EP-A-510,331describes suitable sequestrants derived from collagen, keratin orcasein. EP-A-528,859 describes a suitable alkyl iminodiacetic acidsequestrant. Dipicolinic acid and 2-phosphonobutane-1,2,4-tricarboxylicacid are also suitable. Glycinamide-N,N'-disuccinic acid (GADS),ethylenediamine--N-N'-diglutaric acid (EDDG) and2-hydroxypropylenediamine-N-N'-disuccinic acid (HPDDS) are alsosuitable.

Organic Peroxyacid Bleaching System

A preferred feature of detergent compositions or component thereof inaccordance with the invention is an organic peroxyacid bleaching system.In one preferred execution the bleaching system contains a hydrogenperoxide source and an organic peroxyacid bleach precursor compound. Theproduction of the organic peroxyacid occurs by an in situ reaction ofthe precursor with a source of hydrogen peroxide. Preferred sources ofhydrogen peroxide include inorganic perhydrate bleaches. In analternative preferred execution a preformed organic peroxyacid isincorporated directly into the composition. Compositions containingmixtures of a hydrogen peroxide source and organic peroxyacid precursorin combination with a preformed organic peroxyacid are also envisaged.

Inorganic Perhydrate Bleaches

Inorganic perhydrate salts are a preferred source of hydrogen peroxide.These salts are normally incorporated in the form of the alkali metal,preferably sodium salt at a level of from 1% to 40% by weight, morepreferably from 2% to 30% by weight and most preferably from 5% to 25%by weight of the compositions.

Examples of inorganic perhydrate salts include perborate, percarbonate,perphosphate, persulfate and persilicate salts. The inorganic perhydratesalts are normally the alkali metal salts. The inorganic perhydrate saltmay be included as the crystalline solid without additional protection.For certain perhydrate salts however, the preferred executions of suchgranular compositions utilize a coated form of the material whichprovides better storage stability for the perhydrate salt in thegranular product and/or delayed release of the perhydrate salt oncontact of the granular product with water. Suitable coatings compriseinorganic salts such as alkali metal silicate, carbonate or borate saltsor mixtures thereof, or organic materials such as waxes, oils, or fattysoaps.

Sodium perborate is a preferred perhydrate salt and can be in the formof the monohydrate of nominal formula NaBO₂ H₂ O₂ or the tetrahydrateNaBO₂ H₂ O₂.3H₂ O.

Alkali metal percarbonates, particularly sodium percarbonate arepreferred perhydrates herein. Sodium percarbonate is an additioncompound having a formula corresponding to 2Na₂ CO₃.3H₂ O₂, and isavailable commercially as a crystalline solid.

Potassium peroxymonopersulfate is another inorganic perhydrate salt ofuse in the detergent compositions herein.

Peroxyacid Bleach Precursor

Peroxyacid bleach precursors are compounds which react with hydrogenperoxide in a perhydrolysis reaction to produce a peroxyacid. Generallyperoxyacid bleach precursors may be represented as ##STR1## where L is aleaving group and X is essentially any functionality, such that onperhydrolysis the structure of the peroxyacid produced is ##STR2##

Peroxyacid bleach precursor compounds are preferably incorporated at alevel of from 0.5% to 20% by weight, more preferably from 1% to 15% byweight, most preferably from 1.5% to 10% by weight of the detergentcompositions.

Suitable peroxyacid bleach precursor compounds typically contain one ormore N--or O-acyl groups, which precursors can be selected from a widerange of classes. Suitable classes include anhydrides, esters, imides,lactams and acylated derivatives of imidazoles and oximes. Examples ofuseful materials within these classes are disclosed in GB-A-1586789.Suitable esters are disclosed in GB-A-836988, 864798, 1147871, 2143231and EP-A-0170386.

Leaving Groups

The leaving group, hereinafter L group, must be sufficiently reactivefor the perhydrolysis reaction to occur within the optimum time frame(e.g., a wash cycle). However, if L is too reactive, this activator willbe difficult to stabilize for use in a bleaching composition.

Preferred L groups are selected from the group consisting of: ##STR3##and mixtures thereof, wherein R¹ is an alkyl, aryl, or alkaryl groupcontaining from 1 to 14 carbon atoms, R³ is an alkyl chain containingfrom 1 to 8 carbon atoms, R⁴ is H or R³, R⁵ is an alkenyl chaincontaining from 1 to 8 carbon atoms and Y is H or a solubilizing group.Any of R¹, R³ and R⁴ may be substituted by essentially any functionalgroup including, for example alkyl, hydroxy, alkoxy, halogen, amine,nitrosyl, amide and ammonium or alkyl ammonium groups.

The preferred solubilizing groups are --SO₃ ⁻ M⁺, --CO₂ ⁻ M⁺, --SO₄ ⁻M⁺, --N⁺ (R³)₄ X⁻ and O<--N(R³)₃ and most preferably --SO₃ ⁻ M⁺ and--CO₂ ⁻ M⁺ wherein R³ is an alkyl chain containing from 1 to 4 carbonatoms, M is a cation which provides solubility to the bleach activatorand X is an anion which provides solubility to the bleach activator.Preferably, M is an alkali metal, ammonium or substituted ammoniumcation, with sodium and potassium being most preferred, and X is ahalide, hydroxide, methylsulfate or acetate anion.

Alkyl Percarboxylic Acid Bleach Precursors

Alkyl percarboxylic acid bleach precursors form percarboxylic acids onperhydrolysis. Preferred precursors of this type provide peracetic acidon perhydrolysis.

Preferred alkyl percarboxylic precursor compounds of the imide typeinclude the N--,N,N¹ N¹ tetra acetylated alkylene diamines wherein thealkylene group contains from 1 to 6 carbon atoms, particularly thosecompounds in which the alkylene group contains 1, 2 and 6 carbon atoms.Tetraacetyl ethylene diamine (TAED) is particularly preferred.

Other preferred alkyl percarboxylic acid precursors include sodium3,5,5-tri-methyl hexanoyloxybenzene sulfonate (iso-HOBS), sodiumnonanoyloxybenzene sulfonate (NOBS), sodium acetoxybenzene sulfonate(ABS) and pentaacetyl glucose.

Amide Substituted Alkyl Peroxyacid Precursors

Amide substituted alkyl peroxyacid precursor compounds are suitableherein, including those of the following general formulae: ##STR4##wherein R¹ is an alkyl group with from 1 to 14 carbon atoms, R² is analkylene group containing from 1 to 14 carbon atoms, and R⁵ is H or analkyl group containing 1 to 10 carbon atoms and L can be essentially anyleaving group. Amide substituted bleach activator compounds of this typeare described in EP-A-0170386.

Perbenzoic Acid Precursor

Perbenzoic acid precursor compounds provide perbenzoic acid onperhydrolysis. Suitable O-acylated perbenzoic acid precursor compoundsinclude the substituted and unsubstituted benzoyl oxybenzene sulfonates,and the benzoylation products of sorbitol, glucose, and all saccharideswith benzoylating agents, and those of the imide type includingN-benzoyl succinimide, tetrabenzoyl ethylene diamine and the N-benzoylsubstituted ureas. Suitable imidazole type perbenzoic acid precursorsinclude N-benzoyl imidazole and N-benzoyl benzimidazole. Other usefulN-acyl group-containing perbenzoic acid precursors include N-benzoylpyrrolidone, dibenzoyl taurine and benzoyl pyroglutamic acid.

Cationic Peroxyacid Precursors

Cationic peroxyacid precursor compounds produce cationic peroxyacids onperhydrolysis.

Typically, cationic peroxyacid precursors are formed by substituting theperoxyacid part of a suitable peroxyacid precursor compound with apositively charged functional group, such as an ammonium or alkylammonium group, preferably an ethyl or methyl ammonium group. Cationicperoxyacid precursors are typically present in the solid detergentcompositions as a salt with a suitable anion, such as a halide ion.

The peroxyacid precursor compound to be so cationically substituted maybe a perbenzoic acid, or substituted derivative thereof, precursorcompound as described hereinbefore. Alternatively, the peroxyacidprecursor compound may be an alkyl percarboxylic acid precursor compoundor an amide substituted alkyl peroxyacid precursor as describedhereinafter

Cationic peroxyacid precursors are described in U.S. Pat. Nos.4,904,406; 4,751,015; 4,988,451; 4,397,757; 5,269,962; 5,127,852;5,093,022; 5,106,528; U.K. 1,382,594; EP 475,512, 458,396 and 284,292;and in JP 87-318,332.

Examples of preferred cationic peroxyacid precursors are described in UKPatent Application No. 9407944.9 and U.S. patent application Ser. Nos.08/298,903, 08/298,650, 08/298,904 and 08/298,906.

Suitable cationic peroxyacid precursors include any of the ammonium oralkyl ammonium substituted alkyl or benzoyl oxybenzene sulfonates,N-acylated caprolactams, and monobenzoyltetraacetyl glucose benzoylperoxides. Preferred cationic peroxyacid precursors of the N-acylatedcaprolactam class include the trialkyl ammonium methylene benzoylcaprolactams and the trialkyl ammonium methylene alkyl caprolactams.

Benzoxazin Organic Peroxyacid Precursors

Also suitable are precursor compounds of the benzoxazin-type, asdisclosed for example in EP-A-332,294 and EP-A-482,807, particularlythose having the formula: ##STR5## wherein R₁ is H, alkyl, alkaryl,aryl, or arylalkyl. Preformed Organic Peroxyacid

The organic peroxyacid bleaching system may contain, in addition to, oras an alternative to, an organic peroxyacid bleach precursor compound, apreformed organic peroxyacid, typically at a level of from 1% to 15% byweight, more preferably from 1% to 10% by weight of the composition.

A preferred class of organic peroxyacid compounds are the amidesubstituted compounds of the following general formulae: ##STR6##wherein R¹ is an alkyl, aryl or alkaryl group with from 1 to 14 carbonatoms, R² is an alkylene, arylene, and alkarylene group containing from1 to 14 carbon atoms, and R⁵ is H or an alkyl, aryl, or alkaryl groupcontaining 1 to 10 carbon atoms. Amide substituted organic peroxyacidcompounds of this type are described in EP-A-0170386.

Other organic peroxyacids include diacyl and tetraacylperoxides,especially diperoxydodecanedioc acid, diperoxytetradecanedioic acid anddiperoxyhexadecanedioc acid. Mono- and diperazelaic acid, mono- anddiperbrassylic acid and N-phthaloylaminoperoxicaproic acid are alsosuitable herein.

Bleach Catalyst

The compositions of the invention optionally contain a transition metalcontaining bleach catalyst. One suitable type of bleach catalyst is acatalyst system comprising a heavy metal cation of defined bleachcatalytic activity, such as copper, iron or manganese cations, anauxiliary metal cation having little or no bleach catalytic activity,such as zinc or aluminum cations, and a sequestrant having definedstability constants for the catalytic and auxiliary metal cations,particularly ethylenediaminetetraacetic acid,ethylenediaminetetra(methylenephosphonic acid) and water-soluble saltsthereof. Such catalysts are disclosed in U.S. Pat. No. 4,430,243.

Other types of bleach catalysts include the manganese-based complexesdisclosed in U.S. Pat. No. 5,246,621 and U.S. Pat. No. 5,244,594.Preferred examples of these catalysts include Mn^(IV) ₂ (u-O)₃(1,4,7-trimethyl-1,4,7-triazacyclononane)₂ -(PF₆)₂, Mn^(III) ₂ (u-O)₁(u-OAc)₂ (1,4,7-trimethyl-1,4,7-triazacyclononane)₂ -(ClO₄)₂, Mn^(IV) ₄(u-O)₆ (1,4,7-triazacyclononane)₄ -(ClO₄)₂, Mn^(III) Mn^(IV) ₄ (u-O)₁(u-OAc)₂₋ (1,4,7-trimethyl-1,4,7-triazacyclononane)₂₋ (ClO₄)₃, andmixtures thereof. Others are described in European patent applicationpublication no. 549,272. Other ligands suitable for use herein include1,5,9-trimethyl-1,5,9-triazacyclododecane,2-methyl-1,4,7-triazacyclononane, 2-methyl-1,4,7-triazacyclononane,1,2,4,7-tetramethyl-1,4,7-triazacyclononane, and mixtures thereof.

For examples of suitable bleach catalysts see U.S. Pat. No. 4,246,612and U.S. Pat. No. 5,227,084. See also U.S. Pat. No. 5,194,416 whichteaches mononuclear manganese (IV) complexes such asMn(1,4,7-trimethyl-1,4,7-triazacyclononane)(OCH₃)₃₋ (PF₆). Still anothertype of bleach catalyst, as disclosed in U.S. Pat. No. 5,114,606, is awater-soluble complex of manganese (III), and/or (IV) with a ligandwhich is a non-carboxylate polyhydroxyl compound having at least threeconsecutive C--OH groups. Other examples include binuclear Mn complexedwith tetra-N-dentate and bi-N-dentate ligands, including N₄ Mn^(III)(u-O)₂ Mn^(IV) N₄)⁺ and [Bipy₂ Mn^(III) (u-O)₂ Mn^(IV) bipy₂ ]-(ClO₄)₃.

Further suitable bleach catalysts are described, for example, inEuropean patent application No. 408,131 (cobalt complex catalysts),European patent applications, publication nos. 384,503, and 306,089(metallo-porphyrin catalysts), U.S. Pat. No. 4,728,455(manganese/multidentate ligand catalyst), U.S. Pat. No. 4,711,748 andEuropean patent application, publication no. 224,952, (absorbedmanganese on aluminosilicate catalyst), U.S. Pat. No. 4,601,845(aluminosilicate support with manganese and zinc or magnesium salt),U.S. Pat. No. 4,626,373 (manganese/ligand catalyst), U.S. Pat. No.4,119,557 (ferric complex catalyst), German Pat. specification 2,054,019(cobalt chelant catalyst) Canadian 866,191 (transition metal-containingsalts), U.S. Pat. No. 4,430,243 (chelants with manganese cations andnon-catalytic metal cations), and U.S. Pat. No. 4,728,455 (manganesegluconate catalysts).

Additional Enzymes

The compositions of the present invention may comprise one or moreadditional enzymes.

Preferred additional enzymatic materials include the commerciallyavailable enzymes. Said enzymes include enzymes selected from lipases,cellulases, hemicellulases, peroxidases, proteases, gluco-amylases,amylases, xylanases, phospholipases, esterases, cutinases, pectinases,keratanases, reductases, oxidases, phenoloxidases, lipoxygenases,ligninases, pullulanases, tannases, pentosanases, malanases,β-glucanases, arabinosidases, hyaluronidase, chondroitinase, laccase ormixtures thereof.

A preferred combination of additional enzymes in a detergent compositionaccording to the present invention comprises a mixture of conventionalapplicable enzymes such as protease, amylase, cutinase and/or cellulasein conjunction with one or more plant cell wall degrading enzymes.Suitable enzymes are exemplified in U.S. Pat. Nos. 3,519,570 and3,533,139.

Suitable proteases are the subtilisins which are obtained fromparticular strains of B. subtilis and B. licheniformis (subtilisin BPNand BPN'). One suitable protease is obtained from a strain of Bacillus,having maximum activity throughout the pH range of 8-12, developed andsold as ESPERASE® by Novo Industries A/S of Denmark, hereinafter "Novo".The preparation of this enzyme and analogous enzymes is described in GB1,243,784 to Novo. Other suitable proteases include ALCALASE®, DURAZYM®and SAVINASE® from Novo and MAXATASE®, MAXACAL®, PROPERASE® and MAXAPEM®(protein engineered Maxacal) from Gist-Brocades. Proteolytic enzymesalso encompass modified bacterial serine proteases, such as thosedescribed in European Patent Application Serial Number 87 303761.8,filed Apr. 28, 1987 (particularly pages 17, 24 and 98), and which iscalled herein "Protease B", and in European Patent Application 199,404,Venegas, published Oct. 29, 1986, which refers to a modified bacterialserine protealytic enzyme which is called "Protease A" herein. Suitableis what is called herein "Protease C", which is a variant of an alkalineserine protease from Bacillus in which lysine replaced arginine atposition 27, tyrosine replaced valine at position 104, serine replacedasparagine at position 123, and alanine replaced threonine at position274. Protease C is described in EP 90915958:4, corresponding to WO91/06637, Published May 16, 1991. Genetically modified variants,particularly of Protease C, are also included herein.

A preferred protease referred to as "Protease D" is a carbonyl hydrolasevariant having an amino acid sequence not found in nature, which isderived from a precursor carbonyl hydrolase by substituting a differentamino acid for a plurality of amino acid residues at a position in saidcarbonyl hydrolase equivalent to position +76, preferably also incombination with one or more amino acid residue positions equivalent tothose selected from the group consisting of +99, +101, +103, +104, +107,+123, +27, +105, +109, +126, +128, +135, +156, +166, +195, +197, +204,+206, +210, +216, +217, +218, +222, +260, +265, and/or +274 according tothe numbering of Bacillus amyloliquefaciens subtilisin, as described inWO95/10591 and in the patent application of C. Ghosh, et al, "BleachingCompositions Comprising Protease Enzymes" having U.S. Ser. No.08/322,677, filed Oct. 13, 1994.

Also suitable for the present invention are proteases described inpatent applications EP 251 446 and WO 91/06637, protease BLAP® describedin WO91/02792 and their variants described in WO 95/23221.

See also a high pH protease from Bacillus sp. NCIMB 40338 described inWO 93/18140 A to Novo. Enzymatic detergents comprising protease, one ormore other enzymes, and a reversible protease inhibitor are described inWO 92/03529 A to Novo. When desired, a protease having decreasedadsorption and increased hydrolysis is available as described in WO95/07791 to Procter & Gamble. A recombinant trypsin-like protease fordetergents suitable herein is described in WO 94/25583 to Novo. Othersuitable proteases are described in EP 516 200 by Unilever.

One or a mixture of proteolytic enzymes may be incorporated in thedetergent compositions of the present invention, generally at a level offrom 0.0001% to 2%, preferably from 0.001% to 0.2%, more preferably from0.005% to 0.1% pure enzyme by weight of the composition.

In the detergent compositions of the present invention, the lipolyticenzyme component is generally present at levels of from 0.00005% to 2%of active enzyme by weight of the detergent composition, preferably0.001% to 1% by weight, most preferably from 0.0002% to 0.05% by weightactive enzyme in the detergent composition.

Suitable lipolytic enzymes for use in the present invention includethose produced by micro-organisms of the Pseudomonas group, such asPseudomonas stutzeri ATCC 19.154, as disclosed in British Patent1,372,034. Suitable lipases include those which show a positiveimmunological cross-section with the antibody of the lipase produced bythe microorganism Pseudomonas Hisorescent IAM 1057. This lipase isavailable from Amano Pharmaceutical Co. Ltd., Nagoya, Japan, under thetrade name Lipase P "Amano," hereinafter referred to as "Amano-P." Othersuitable commercial lipases include Amano-CES, lipases ex Chromobacterviscosum, e.g. Chromobacter viscosum var. lipolyticum NRRLB 3673,commercially available from Toyo Jozo Co., Tagata, Japan; Chromobacterviscosum lipases from U.S. Biochemical Corp., U.S.A. and Disoynth Co.,The Netherlands, and lipases ex Pseudomonas gladioli. Especiallysuitable lipases are lipases such as M1 Lipase^(R) and Lipomax^(R)(Gist-Brocades) and Lipolase^(R) and Lipolase Ultra^(R) (Novo) whichhave found to be very effective when used in combination with thecompositions of the present invention. Also suitable are the lipolyticenzymes described in EP 258 068, WO 92/05249 and WO 95/22615 by NovoNordisk and in WO 94/03578, WO 95/35381 and WO 96/00292 by Unilever.

Also suitable are cutinases [EC 3.1.1.50] which can be considered as aspecial kind of lipase, namely lipases which do not require interfacialactivation. Addition of cutinases to detergent compositions have beendescribed in e.g. WO-A-88/09367 (Genencor); WO 90/09446 (Plant GeneticSystem) and WO 94/14963 and WO 94/14964 (Unilever). The LIPOLASE enzymederived from Humicola lanuginosa and commercially available from Novo(see also EPO 341,947) is a preferred lipase for use in the presentinvention.

Another preferred lipase for use in the present invention is D96Llipolytic enzyme variant of the native lipase derived from Humicolalanuginosa. Most preferably the Humicola lanuginosa strain DSM 4106 isused.

By D96L lipolytic enzyme variant is meant the lipase variant asdescribed in patent application WO 92/05249 in which the native lipaseex Humicola lanuginosa has the aspartic acid (D) residue at position 96changed to Leucine (L). According to this nomenclature said substitutionof aspartic acid to Leucine in position 96 is shown as: D96L. Todetermine the activity of the enzyme D96L the standard LU assay may beused (Analytical method, internal Novo Nordisk number AF 95/6-GB1991.02.07). A substrate for D96L was prepared by emulsifying glycerinetributyrate (Merck) using gum-arabic as emulsifier. Lipase activity isassayed at pH 7 using pH stat. method.

The detergent compositions of the invention may also contain one or amixture of more than one amylase enzyme (α and/or β). WO94/02597, NovoNordisk A/S published Feb. 03, 1994, describes cleaning compositionswhich incorporate mutant amylases. See also WO95/10603, Novo NordiskA/S, published Apr. 20, 1995. Other amylases known for use in cleaningcompositions include both α- and β-amylases. α-Amylases are known in theart and include those disclosed in U.S. Pat. No. 5,003,257; EP 252,666;WO/91/00353; FR 2,676,456; EP 285,123; EP 525,610; EP 368,341; andBritish Patent specification no. 1,296,839 (Novo). Other suitableamylases are stability-enhanced amylases described in WO94/18314,published Aug. 18, 1994 and WO96/05295, Genencor, published Feb. 22,1996 and amylase variants having additional modification in theimmediate parent available from Novo Nordisk A/S, disclosed in WO95/10603, published April 95. Also suitable are amylases described in EP277 216, WO95/26397 and WO96/23873 (all by Novo Nordisk).

Examples of commercial α-amylases products are Purafect Ox Am® fromGenencor and Termamyl®, Ban®,Fungamyl® and Duramyl®, all available fromNovo Nordisk A/S Denmark. WO95/26397 describes other suitable amylases:α-amylases characterised by having a specific activity at least 25%higher than the specific activity of Termamyl® at a temperature range of25° C. to 55° C. and at a pH value in the range of 8 to 10, measured bythe Phadebas® α-amylase activity assay. Suitable are variants of theabove enzymes, described in WO96/23873 (Novo Nordisk). Other preferredamylolytic enzymes with improved properties with respect to the activitylevel and the combination of thermostability and a higher activity levelare described in WO95/35382.

The amylolytic enzymes if present are generally incorporated in thedetergent compositions of the present invention a level of from 0.0001%to 2%, preferably from 0.00018% to 0.06%, more preferably from 0.00024%to 0.048% pure enzyme by weight of the composition.

The detergent compositions of the invention may additionally incorporateone or more cellulase enzymes. Suitable cellulases include bothbacterial or fungal cellulases. Preferably, they will have a pH optimumof between 5 and 12 and an activity above 50 CEVU (Cellulose ViscosityUnit). Suitable cellulases are disclosed in U.S. Pat. No. 4,435,307,Barbesgoard et al, J61078384 and WO96/02653 which disclose fungalcellulases produced respectively from Humicola insolens, Trichoderma,Thielavia and Sporotrichum. EP 739 982 describes cellulases isolatedfrom novel Bacillus species. Suitable cellulases are also disclosed inGB-A-2.075.028; GB-A-2.095.275; DE-OS-2.247.832 and WO95126398.

Examples of such cellulases are cellulases produced by a strain ofHumicola insolens (Humicola grisea var. thermoidea), particularly theHumicola strain DSM 1800. Other suitable cellulases are cellulasesoriginated from Humicola insolens having a molecular weight of about50KDa, an isoelectric point of 5.5 and containing 415 amino acids; and a˜43kD endoglucanase derived from Humicola insolens, DSM 1800, exhibitingcellulase activity; a preferred endoglucanase component has the aminoacid sequence disclosed in PCT Patent Application No. WO 91/17243. Alsosuitable cellulases are the EGIII cellulases from Trichodermalongibrachiatum described in WO94/21801, Genencor, published Sep. 29,1994. Especially suitable cellulases are the cellulases having colorcare benefits. Examples of such cellulases are cellulases described inEuropean patent application No. 91202879.2, filed Nov. 6, 1991 (Novo).Carezyme and Celluzyme (Novo Nordisk A/S) are especially useful. Seealso WO91/17244 and WO91/21801. Other suitable cellulases for fabriccare and/or cleaning properties are described in WO96/34092, WO96/17994and WO95/24471.

Peroxidase enzymes may also be incorporated into the detergentcompositions of the invention. Peroxidasis are used in combination withoxygen sources, e.g. percarbonate, perborate, persulfate, hydrogenperoxide, etc. They are used for "solution bleaching", i.e. to preventtransfer of dyes or pigments removed from substrates during washoperations to other substrates in the wash solution. Peroxidase enzymesare known in the art, and include, for example, horseradish peroxidase,ligninase and haloperoxidase such as chloro- and bromo-peroxidase.Peroxidase-containing detergent compositions are disclosed, for example,in PCT International Application WO 89/099813, WO89/09813 and inEuropean Patent application EP No. 91202882.6, filed on Nov. 6, 1991 andEP No. 96870013.8, filed Feb. 20, 1996. Also suitable is the laccaseenzyme.

Preferred enhancers are substituted phenthiazine and phenoxasine10-Phenothiazinepropionicacid (PPT), 10-ethylphenothiazine-4-carboxylicacid (EPC), 10-phenoxazinepropionic acid (POP) and 10-methylphenoxazine(described in WO 94/12621) and substituted syringates (C3-C5 substitutedalkyl syringates) and phenols. Sodium percarbonate or perborate arepreferred sources of hydrogen peroxide.

Said cellulases and/or peroxidases, if present, are normallyincorporated in the detergent composition at levels from 0.0001% to 2%of active enzyme by weight of the detergent composition.

Said additional enzymes, when present, are normally incorporated in thedetergent composition at levels from 0.0001% to 2% of active enzyme byweight of the detergent composition. The additional enzymes can be addedas separate single ingredients (prills, granulates, stabilized liquids,etc. containing one enzyme) or as mixtures of two or more enzymes (e.g.cogranulates

Enzyme Oxidation Scavengers

Other suitable detergent ingredients that can be added are enzymeoxidation scavengers which are described in Copending European Patentapplication 92870018.6 filed on Jan. 31, 1992. Examples of such enzymeoxidation scavengers are ethoxylated tetraethylene polyamines.

Enzyme Materials

A range of enzyme materials and means for their incorporation intosynthetic detergent compositions is also disclosed in WO 9307263 A andWO 9307260 A to Genencor International, WO 8908694 A to Novo, and U.S.Pat. No. 3,553,139, Jan. 5, 1971 to McCarty et al. Enzymes are furtherdisclosed in U.S. Pat. No. 4,101,457, Place et al, Jul. 18, 1978, and inU.S. Pat. No. 4,507,219, Hughes, Mar. 26, 1985. Enzyme materials usefulfor liquid detergent formulations, and their incorporation into suchformulations, are disclosed in U.S. Pat. No. 4,261,868, Hora et al, Apr.14, 1981. Enzymes for use in detergents can be stabilised by varioustechniques. Enzyme stabilisation techniques are disclosed andexemplified in U.S. Pat. No. 3,600,319, Aug. 17, 1971, Gedge et al, EP199,405 and EP 200,586, Oct. 29, 1986, Venegas. Enzyme stabilisationsystems are also described, for example, in U.S. Pat. No. 3,519,570. Auseful Bacillus, sp. AC13 giving proteases, xylanases and cellulases, isdescribed in WO 9401532 A to Novo.

Organic Polymeric Compound

Organic polymeric compounds are preferred additional components of thedetergent compositions or components thereof of the present invention,and are preferably present as components of any particulate component ofthe detergent composition where they may act such as to bind theparticulate component together. By organic polymeric compound is meantany polymeric organic compound commonly used as dispersants,anti-redeposition or soil suspension agents in detergent compositions,including any of the high molecular weight organic polymeric compoundsdescribed as clay flocculating agents herein.

Such an organic polymeric compound is generally incorporated in thedetergent compositions of the invention at a level of from 0.1% to 30%,preferably from 0.5% to 15%, most preferably from 1% to 10% by weight ofthe compositions.

Examples of organic polymeric compounds include the water solubleorganic homo- or co-polymeric polycarboxylic acids or their salts inwhich the polycarboxylic acid comprises at least two carboxyl radicalsseparated from each other by not more than two carbon atoms. Polymers ofthe latter type are disclosed in GB-A-1,596,756. Examples of such saltsare polyacrylic acid or polyacrylates of MWt 1000-5000 and theircopolymers with maleic anhydride, such copolymers having a molecularweight of from 2000 to 100,000, especially 40,000 to 80,000.Polymaleates or polymaleic acid polymers and salts thereof are alsosuitable examples.

Polyamino compounds useful herein include those derived from asparticacid including polyaspartic acid and such as those disclosed inEP-A-305282, EP-A-305283 and EP-A-351629.

Terpolymers containing monomer units selected from maleic acid, acrylicacid, aspartic acid and vinyl alcohol or acetate, particularly thosehaving an average molecular weight of from 1,000 to 30,000, preferably3,000 to 10,000, are also suitable for incorporation into thecompositions of the present invention.

Other organic polymeric compounds suitable for incorporation in thedetergent compositions of the present invention include cellulosederivatives such as methylcellulose, carboxymethylcellulose,hydroxypropylmethylcellulose, ethylhydroxyethylcellulose andhydroxyethylcellulose.

Further useful organic polymeric compounds are the polyethylene glycols,particularly those of molecular weight 1000 to 10000, more particularly2000 to 8000 and most preferably about 4000.

Cationic Soil Removal/Anti-redeposition Compounds

The detergent composition or components thereof of the invention maycomprise water-soluble cationic ethoxylated amine compounds withparticulate soil/clay-soil removal and/or anti-redeposition propertieswhich may act as the cationic dye-fixing agent. These cationic compoundsare described in more detail in EP-B-1 11965, U.S. Pat. No. 4,659,802and U.S. Pat. No. 4,664,848. Particularly preferred of these cationiccompounds are ethoxylated cationic monoamines, diamines or triamines.Especially preferred are the ethoxylated cationic monoamines, diaminesand triamines of the formula: ##STR7## wherein X is a nonionic groupselected from the group consisting of H, C₁ -C₄ alkyl or hydroxyalkylester or ether groups, and mixtures thereof, a is from 0 to 20,preferably from 0 to 4 (e.g. ethylene, propylene, hexamethylene) b is 2,1 or 0; for cationic monoamines (b=0), n is preferably at least 16, witha typical range of from 20 to 35; for cationic diamines or triamines, nis preferably at least about 12 with a typical range of from about 12 toabout 42.

These compounds where present in the composition, are generally presentin an amount of from 0.01 to 30% by weight, preferably 0.05 to 10% byweight.

Suds Suppressing System

The detergent compositions of the invention, when formulated for use inmachine washing compositions, preferably comprise a suds suppressingsystem present at a level of from 0.01% to 15%, preferably from 0.05% to10%, most preferably from 0.1% to 5% by weight of the composition.

Suitable suds suppressing systems for use herein may compriseessentially any known antifoam compound, including, for example siliconeantifoam compounds and 2-alkyl alcanol antifoam compounds.

By antifoam compound it is meant herein any compound or mixtures ofcompounds which act such as to depress the foaming or sudsing producedby a solution of a detergent composition, particularly in the presenceof agitation of that solution.

Particularly preferred antifoam compounds for use herein are siliconeantifoam compounds defined herein as any antifoam compound including asilicone component. Such silicone antifoam compounds also typicallycontain a silica component. The term "silicone" as used herein, and ingeneral throughout the industry, encompasses a variety of relativelyhigh molecular weight polymers containing siloxane units and hydrocarbylgroup of various types. Preferred silicone antifoam compounds are thesiloxanes, particularly the polydimethylsiloxanes having trimethylsilylend blocking units.

Other suitable antifoam compounds include the monocarboxylic fatty acidsand soluble salts thereof. These materials are described in U.S. Pat.No. 2,954,347, issued Sep. 27, 1960 to Wayne St. John. Themonocarboxylic fatty acids, and salts thereof, for use as sudssuppressor typically have hydrocarbyl chains of 10 to 24 carbon atoms,preferably 12 to 18 carbon atoms.

Suitable salts include the alkali metal salts such as sodium, potassium,and lithium salts, and ammonium and alkanolammonium salts.

Other suitable antifoam compounds include, for example, high molecularweight fatty esters (e.g. fatty acid triglycerides), fatty acid estersof monovalent alcohols, aliphatic C₁₈ -C₄₀ ketones (e.g. stearone)N-alkylated amino triazines such as tri- to hexa-alkylmelamines or di-to tetra alkyldiamine chlortriazines formed as products of cyanuricchloride with two or three moles of a primary or secondary aminecontaining 1 to 24 carbon atoms, propylene oxide, bis stearic acid amideand monostearyl di-alkali metal (e.g. sodium, potassium, lithium)phosphates and phosphate esters.

A preferred suds suppressing system comprises

(a) antifoam compound, preferably silicone antifoam compound, mostpreferably a silicone antifoam compound comprising in combination

(i) polydimethyl siloxane, at a level of from 50% to 99%, preferably 75%to 95% by weight of the silicone antifoam compound; and

(ii) silica, at a level of from 1% to 50%, preferably 5% to 25% byweight of the silicone/silica antifoam compound;

wherein said silica/silicone antifoam compound is incorporated at alevel of from 5% to 50%, preferably 10% to 40% by weight;

(b) a dispersant compound, most preferably comprising a silicone glycolrake copolymer with a polyoxyalkylene content of 72-78% and an ethyleneoxide to propylene oxide ratio of from 1:0.9 to 1:1.1, at a level offrom 0.5% to 10%, preferably 1% to 10% by weight; a particularlypreferred silicone glycol rake copolymer of this type is DCO₅₄₄,commercially available from DOW Corning under the tradename DCO_(544;)

(c) an inert carrier fluid compound, most preferably comprising a C₁₆-C₁₈ ethoxylated alcohol with a degree of ethoxylation of from 5 to 50,preferably 8 to 15, at a level of from 5% to 80%, preferably 10% to 70%,by weight;

A highly preferred particulate suds suppressing system is described inEP-A-0210731 and comprises a silicone antifoam compound and an organiccarrier material having a melting point in the range 50° C. to 85° C.,wherein the organic carrier material comprises a monoester of glyceroland a fatty acid having a carbon chain containing from 12 to 20 carbonatoms. EP-A-0210721 discloses other preferred particulate sudssuppressing systems wherein the organic carrier material is a fatty acidor alcohol having a carbon chain containing from 12 to 20 carbon atoms,or a mixture thereof, with a melting point of from 45° C. to 80° C.

Polymeric Dye Transfer Inhibiting Agents

The detergent compositions herein may also comprise from 0.01% to 10%,preferably from 0.05% to 0.5% by weight of polymeric dye transferinhibiting agents.

The polymeric dye transfer inhibiting agents are preferably selectedfrom polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone andN-vinylimidazole, polyvinylpyrrolidone polymers or combinations thereof,whereby these polymers can be cross-linked polymers.

a) Polyamine N-oxide Polymers

Polyamine N-oxide polymers suitable for use herein contain units havingthe following structure formula: ##STR8## wherein P is a polymerisableunit, and ##STR9## R¹ is H or C₁₋₆ linear or branched alkyl; or may forma heterocyclic group with R;

R are aliphatic, ethoxylated aliphatics, aromatic, heterocyclic oralicyclic groups or any combination thereof whereto the nitrogen of theN--O group can be attached or wherein the nitrogen of the N--O group ispart of these groups.

The N--O group can be represented by the following general structures:##STR10## wherein R1, R2, and R3 are aliphatic groups, aromatic,heterocyclic or alicyclic groups or combinations thereof, x or/and yor/and z is 0 or 1 and wherein the nitrogen of the N--O group can beattached or wherein the nitrogen of the N--O group forms part of thesegroups. The N--O group can be part of the polymerisable unit (P) or canbe attached to the polymeric backbone or a combination of both.

Suitable polyamine N-oxides wherein the N--O group forms part of thepolymerisable unit comprise polyamine N-oxides wherein R is selectedfrom aliphatic, aromatic, alicyclic or heterocyclic groups. One class ofsaid polyamine N-oxides comprises the group of polyamine N-oxideswherein the nitrogen of the N--O group forms part of the R-group.Preferred polyamine N-oxides are those wherein R is a heterocyclic groupsuch as pyridine, N-substituted pyrrole, imidazole, N-substitutedpyrrolidine, piperidine, quinoline, acridine and derivatives thereof.

Other suitable polyamine N-oxides are the polyamine oxides whereto theN--O group is attached to the polymerisable unit. A preferred class ofthese polyamine N-oxides comprises the polyamine N-oxides having thegeneral formula (I) wherein R is an aromatic, heterocyclic or alicyclicgroups wherein the nitrogen of the N--O functional group is part of saidR group. Examples of these classes are polyamine oxides wherein R is aheterocyclic compound such as pyridine, N-substituted pyrrole, imidazoleand derivatives thereof.

The polyamine N-oxides can be obtained in almost any degree ofpolymerisation. The degree of polymerisation is not critical providedthe material has the desired water-solubility and dye-suspending power.Typically, the average molecular weight is within the range of 500 to1000,000.

b) Copolymers of N-vinylpyrrolidone and N-vinylimidazole

Suitable herein are copolymers of N-vinylimidazole andN-vinylpyrrolidone having a preferred average molecular weight range offrom 5,000 to 100,000, or 5,000 to 50,000. The preferred copolymers havea molar ratio of N-vinylimidazole to N-vinylpyrrolidone from 1 to 0.2.

c) Polyvinylpyrrolidone

The detergent compositions herein may also utilize polyvinylpyrrolidone("PVP") having an average molecular weight of from 2,500 to 400,000.Suitable polyvinylpyrrolidones are commercially available from ISPCorporation, New York, N.Y. and Montreal, Canada under the product namesPVP K-15 (viscosity molecular weight of 10,000), PVP K-30 (averagemolecular weight of 40,000), PVP K-60 (average molecular weight of160,000), and PVP K-90 (average molecular weight of 360,000). PVP K-15is also available from ISP Corporation. Other suitablepolyvinylpyrrolidones which are commercially available from BASFCorporation include Sokalan HP 165 and Sokalan HP 12.

d) Polyvinyloxazolidone

The detergent compositions herein may also utilize polyvinyloxazolidonesas polymeric dye transfer inhibiting agents. Said polyvinyloxazolidoneshave an average molecular weight of from 2,500 to 400,000.

e) Polyvinylimidazole

The detergent compositions herein may also utilize polyvinylimidazole aspolymeric dye transfer inhibiting agent. Said polyvinylimidazolespreferably have an average molecular weight of from 2,500 to 400,000.

Optical Brightener

The detergent compositions herein also optionally contain from about0.005% to 5% by weight of certain types of hydrophilic opticalbrighteners.

Hydrophilic optical brighteners useful herein include those having thestructural formula: ##STR11## wherein R₁ is selected from anilino,N-2-bis-hydroxyethyl and NH-2-hydroxyethyl; R₂ is selected fromN-2-bis-hydroxyethyl, N-2-hydroxyethyl-N-methylamino, morphilino, chloroand amino; and M is a salt-forming cation such as sodium or potassium.

When in the above formula, R₁ is anilino, R₂ is N-2-bis-hydroxyethyl andM is a cation such as sodium, the brightener is4,4',-bis[(4-anilino-6-(N-2-bis-hydroxyethyl)-s-triazine-2-yl)amino]-2,2'-stilbenedisulfonicacid and disodium salt. This particular brightener species iscommercially marketed under the tradename Tinopal-UNPA-GX by Ciba-GeigyCorporation. Tinopal-UNPA-GX is the preferred hydrophilic opticalbrightener useful in the detergent compositions herein.

When in the above formula, R₁ is anilino, R₂ isN-2-hydroxyethyl-N-2-methylamino and M is a cation such as sodium, thebrightener is4,4'-bis[(4-anilino-6-(N-2-hydroxyethyl-N-methylamino)-s-triazine-2-yl)amino]2,2'-stilbenedisulfonicacid disodium salt. This particular brightener species is commerciallymarketed under the tradename Tinopal 5BM-GX by Ciba-Geigy Corporation.

When in the above formula, R₁ is anilino, R₂ is morphilino and M is acation such as sodium, the brightener is4,4'-bis[(4-anilino-6-morphilino-s-triazine-2-yl)amino]2,2'-stilbenedisulfonicacid, sodium salt. This particular brightener species is commerciallymarketed under the tradename Tinopal AMS-GX by Ciba Geigy Corporation.

Polymeric Soil Release Agent

Known polymeric soil release agents, hereinafter "SRA", can optionallybe employed in the present detergent compositions. If utilized, SRA'swill generally comprise from 0.01% to 10.0%, typically from 0.1% to 5%,preferably from 0.2% to 3.0% by weight, of the compositions.

Preferred SRA's typically have hydrophilic segments to hydrophilize thesurface of hydrophobic fibers such as polyester and nylon, andhydrophobic segments to deposit upon hydrophobic fibers and remainadhered thereto through completion of washing and rinsing cycles,thereby serving as an anchor for the hydrophilic segments. This canenable stains occurring subsequent to treatment with the SRA to be moreeasily cleaned in later washing procedures.

Preferred SRA's include oligomeric terephthalate esters, typicallyprepared by processes involving at least onetransesterification/oligomerization, often with a metal catalyst such asa titanium(IV) alkoxide. Such esters may be made using additionalmonomers capable of being incorporated into the ester structure throughone, two, three, four or more positions, without, of course, forming adensely crosslinked overall structure.

Suitable SRA's include a sulfonated product of a substantially linearester oligomer comprised of an oligomeric or polymeric ester backbone ofterephthaloyl and oxyalkyleneoxy repeat units and allyl-derivedsulfonated terminal moieties covalently attached to the backbone, forexample as described in U.S. Pat. No. 4,968,451, Nov. 6, 1990 to J. J.Scheibel and E. P. Gosselink. Such ester oligomers can be prepared by:(a) ethoxylating allyl alcohol; (b) reacting the product of (a) withdimethyl terephthalate ("DMT") and 1,2-propylene glycol ("PG") in atwo-stage transesterification/oligomerization procedure; and (c)reacting the product of (b) with sodium metabisulfite in water. OtherSRA's include the nonionic end-capped 1,2-propylene/polyoxyethyleneterephthalate polyesters of U.S. Pat. No. 4,711,730, Dec. 8, 1987 toGosselink et al., for example those produced bytransesterification/oligomerization of poly-(ethyleneglycol) methylether, DMT, PG and poly(ethyleneglycol) ("PEG"). Other examples of SRA'sinclude: the partly- and fully-anionic-end-capped oligomeric esters ofU.S. Pat. No. 4,721,580, Jan. 26, 1988 to Gosselink, such as oligomersfrom ethylene glycol ("EG"), PG, DMT andNa-3,6-dioxa-8-hydroxyoctanesulfonate; the nonionic-capped blockpolyester oligomeric compounds of U.S. Pat. No. 4,702,857, Oct. 27, 1987to Gosselink, for example produced from DMT, methyl (Me)-capped PEG andEG and/or PG, or a combination of DMT, EG and/or PG, Me-capped PEG andNa-dimethyl-5-sulfoisophthalate; and the anionic, especially sulfoaroyl,end-capped terephthalate esters of U.S. Pat. No. 4,877,896, Oct. 31,1989 to Maldonado, Gosselink et al., the latter being typical of SRA'suseful in both laundry and fabric conditioning products, an examplebeing an ester composition made from m-sulfobenzoic acid monosodiumsalt, PG and DMT, optionally but preferably further comprising addedPEG, e.g., PEG 3400.

SRA's also include: simple copolymeric blocks of ethylene terephthalateor propylene terephthalate with polyethylene oxide or polypropyleneoxide terephthalate, see U.S. Pat. No. 3,959,230 to Hays, May 25, 1976and U.S. Pat. No. 3,893,929 to Basadur, Jul. 8, 1975; cellulosicderivatives such as the hydroxyether cellulosic polymers available asMETHOCEL from Dow; the C₁ -C₄ alkyl celluloses and C₄ hydroxyalkylcelluloses, see U.S. Pat. No. 4,000,093, Dec. 28, 1976 to Nicol, et al.;and the methyl cellulose ethers having an average degree of substitution(methyl) per anhydroglucose unit from about 1.6 to about 2.3 and asolution viscosity of from about 80 to about 120 centipoise measured at20° C. as a 2% aqueous solution. Such materials are available asMETOLOSE SM100 and METOLOSE SM200, which are the trade names of methylcellulose ethers manufactured by Shin-etsu Kagaku Kogyo K K.

Additional classes of SRA's include: (I) nonionic terephthalates usingdiisocyanate coupling agents to link polymeric ester structures, seeU.S. Pat. No. 4,201,824, Violland et al. and U.S. Pat. No. 4,240,918Lagasse et al.; and (II) SRA's with carboxylate terminal groups made byadding trimellitic anhydride to known SRA's to convert terminal hydroxylgroups to trimellitate esters. With the proper selection of catalyst,the trimellitic anhydride forms linkages to the terminals of the polymerthrough an ester of the isolated carboxylic acid of trimelliticanhydride rather than by opening of the anhydride linkage. Eithernonionic or anionic SRA's may be used as starting materials as long asthey have hydroxyl terminal groups which may be esterified. See U.S.Pat. No. 4,525,524 Tung et al. Other classes include: (III) anionicterephthalate-based SRA's of the urethane-linked variety, see U.S. Pat.No. 4,201,824, Violland et al.;

Other Optional Ingredients

Other optional ingredients suitable for inclusion in the compositions ofthe invention include perfumes, colours and filler salts, with sodiumsulfate being a preferred filler salt.

Near Neutral Wash pH Detergent Formulation

While the detergent compositions of the present invention are operativewithin a wide range of wash pHs (e.g. from about 5 to about 12), theyare particularly suitable when formulated to provide a near neutral washpH, i.e. an initial pH of from about 7.0 to about 10.5 at aconcentration of from about 0.1 to about 2% by weight in water at 20° C.Near neutral wash pH formulations are better for enzyme stability andfor preventing stains from setting. In such formulations, the wash pH ispreferably from about 7.0 to about 10.5, more preferably from about 8.0to about 10.5, most preferably from 8.0 to 9.0.

Preferred near neutral wash pH detergent formulations are disclosed toEuropean Patent Application 83.200688.6, filed May 16, 1983, J. H. M.Wertz and P. C. E. Goffinet.

Highly preferred compositions of this type also preferably contain fromabout 2 to about 10% by weight of citric acid and minor amounts (e.g.,less than about 20% by weight) of neutralizing agents, buffering agents,phase regulants, hydrotropes, enzymes, enzyme stabilizing agents,polyacids, suds regulants, opacifiers, anti-oxidants, bactericides,dyes, perfumes and brighteners, such as those described in U.S. Pat. No.4,285,841 to Barrat et al., issued Aug. 25, 1981 (herein incorporated byreference).

Form of the Compositions

The compositions in accordance with the invention can take a variety ofphysical forms including granular, tablet, flake, pastille and bar andliquid forms. Liquids may be aqueous or non-aqueous and may be in theform of a gel. The compositions are particularly the so-calledconcentrated granular detergent compositions adapted to be added to awashing machine by means of a dispensing device placed in the machinedrum with the soiled fabric load.

Such granular detergent compositions or components thereof in accordancewith the present invention can be made via a variety of methods,including spray-drying, dry-mixing, extrusion, agglomerating andgranulation. The cationic quaternised surfactant can be added to theother detergent components by mixing, agglomeration (preferably combinedwith a carrier material), granulation or as a spray-dried component.

The compositions in accord with the present invention can also be usedin or in combination with bleach additive compositions, for examplecomprising chlorine bleach.

In one aspect of the invention the mean particle size of the componentsof granular compositions in accordance with the invention, shouldpreferably be such that no more than 15% of the particles are greaterthan 1.8 mm in diameter and not more than 15% of the particles are lessthan 0.25 mm in diameter. Preferably the mean particle size is such thatfrom 10% to 50% of the particles has a particle size of from 0.2 mm to0.7 mm in diameter.

The term mean particle size as defined herein is calculated by sieving asample of the composition into a number of fractions (typically 5fractions) on a series of sieves, preferably Tyler sieves. The weightfractions thereby obtained are plotted against the aperture size of thesieves. The mean particle size is taken to be the aperture size throughwhich 50% by weight of the sample would pass.

In a further aspect of the invention at last 80%, preferably at least90% by weight of the composition comprises particles of mean particlesize at least 0.8 mm, more preferably at least 1.0 mm and mostpreferably from 1.0, or 1.5 to 2.5 mm. Most preferably at least 95% ofthe particles will have such a mean particle size. Such particles arepreferably prepared by an extrusion process.

The bulk density of granular detergent compositions in accordance withthe present invention typically have a bulk density of at least 400,preferably at least 600 g/litre, more preferably from 650 g/litre to1200 g/litre. Bulk density is measured by means of a simple funnel andcup device consisting of a conical funnel moulded rigidly on a base andprovided with a flap valve at its lower extremity to allow the contentsof the funnel to be emptied into an axially aligned cylindrical cupdisposed below the funnel. The funnel is 130 mm high and has internaldiameters of 130 mm and 40 mm at its respective upper and lowerextremities. It is mounted so that the lower extremity is 140 mm abovethe upper surface of the base. The cup has an overall height of 90 mm,an internal height of 87 mm and an internal diameter of 84 mm. Itsnominal volume is 500 ml.

To carry out a measurement, the funnel is filled with powder by handpouring, the flap valve is opened and powder allowed to overfill thecup. The filled cup is removed from the frame and excess powder removedfrom the cup by passing a straight edged implement eg; a knife, acrossits upper edge. The filled cup is then weighed and the value obtainedfor the weight of powder doubled to provide a bulk density in g/litre.Replicate measurements are made as required.

Compacted solids may be manufactured using any suitable compactingprocess, such as tabletting, briquetting or extrusion, preferablytabletting. Preferably tablets for use in dish washing processes, aremanufactured using a standard rotary tabletting press using compressionforces of from 5 to 13 KN/cm², more preferably from 5 to 11 KN/cm² sothat the compacted solid has a minimum hardness of 176N to 275N,preferably from 195N to 245N, measured by a C100 hardness test assupplied by I. Holland instruments. This process may be used to preparehomogeneous or layered tablets of any size or shape. Preferably tabletsare symmetrical to ensure the uniform dissolution of the tablet in thewash solution.

Laundry Washing Rinsing Method

Machine laundry methods herein typically comprise treating soiledlaundry with an aqueous wash solution in a washing machine havingdissolved or dispensed therein an effective amount of a machine laundrydetergent composition in accord with the invention. By an effectiveamount of the detergent composition it is meant from 10 g to 300 g ofproduct dissolved or dispersed in a wash solution of volume from 5 to 65litres, as are typical product dosages and wash solution volumescommonly employed in conventional machine laundry methods. Dosage isdependent upon the particular conditions such as water hardness anddegree of soiling of the soiled laundry.

The detergent composition of the invention may be contacted with thefabric to be treated in a wash step or a rinse step. The detergentcomposition may be dispensed for example, from the drawer dispenser of awashing machine or may be contacted with the fabric to be treated in themachine.

In one use aspect a dispensing device is employed in the washing rinsingmethod. The dispensing device is charged with the detergent product, andis used to introduce the product directly into the drum of the washingmachine before the commencement of the wash or rinse cycle. Its volumecapacity should be such as to be able to contain sufficient detergentproduct as would normally be used in the washing method.

The dispensing device containing the detergent product may be placedinside the drum before the commencement of the wash, before,simultaneously with or after the washing machine has been loaded withlaundry. At the commencement of the wash cycle of the washing machinewater is introduced into the drum and the drum periodically rotates. Thedesign of the dispensing device should be such that it permitscontainment of the dry detergent product but then allows release of thisproduct during the wash cycle in response to its agitation as the drumrotates and also as a result of its contact with the wash water.

To allow for release of the detergent product during the wash or rinse,the device may possess a number of openings through which the productmay pass. Alternatively, the device may be made of a material which ispermeable to liquid but impermeable to the solid product, which willallow release of dissolved product. Preferably, the detergent productwill be rapidly released at the start of the wash cycle therebyproviding transient localised high concentrations of product in the drumof the washing machine at this stage of the wash cycle.

Preferred dispensing devices are reusable and are designed in such a waythat container integrity is maintained in both the dry state and duringthe wash cycle. Especially preferred dispensing devices for use with thecomposition of the invention have been described in the followingpatents; GB-B-2, 157, 717, GB-B-2, 157, 718, EP-A-0201376, EP-A-0288345and EP-A-0288346. An article by J.Bland published in ManufacturingChemist, November 1989, pages 41-46 also describes especially preferreddispensing devices for use with granular laundry products which are of atype commonly know as the "granulette". Another preferred dispensingdevice for use with the compositions of this invention is disclosed inPCT Patent Application No. WO94/11562.

Especially preferred dispensing devices are disclosed in European PatentApplication Publication Nos. 0343069 & 0343070. The latter Applicationdiscloses a device comprising a flexible sheath in the form of a bagextending from a support ring defining an orifice, the orifice beingadapted to admit to the bag sufficient product for one washing cycle ina washing process. A portion of the washing medium flows through theorifice into the bag, dissolves the product, and the solution thenpasses outwardly through the orifice into the washing medium. Thesupport ring is provided with a masking arrangement to prevent egress ofwetted, undissolved, product, this arrangement typically comprisingradially extending walls extending from a central boss in a spoked wheelconfiguration, or a similar structure in which the walls have a helicalform.

Alternatively, the dispensing device may be a flexible container, suchas a bag or pouch. The bag may be of fibrous construction coated with awater impermeable protective material so as to retain the contents, suchas is disclosed in European published Patent Application No. 0018678.Alternatively it may be formed of a water-insoluble synthetic polymericmaterial provided with an edge seal or closure designed to rupture inaqueous media as disclosed in European published Patent Application Nos.0011500, 0011501, 0011502, and 0011968. A convenient form of waterfrangible closure comprises a water soluble adhesive disposed along andsealing one edge of a pouch formed of a water impermeable polymeric filmsuch as polyethylene or polypropylene.

The composition is generally contacted with the laundry or fabric fortreatment at low temperatures of below 40° C. The composition may evenbe contacted with the fabrics to be treated in cold water, for exampleat temperatures below 25° C., or even below 20° C.

Machine Dishwashing Method

Any suitable methods for machine dishwashing or cleaning soiledtableware, particularly soiled silverware are envisaged.

A preferred machine dishwashing method comprises treating soiledarticles selected from crockery, glassware, hollowware, silverware andcutlery and mixtures thereof, with an aqueous liquid having dissolved ordispensed therein an effective amount of a machine dishwashingcomposition in accord with the invention. By an effective amount of themachine dishwashing composition it is meant from 8 g to 60 g of productdissolved or dispersed in a wash solution of volume from 3 to 10 litres,as are typical product dosages and wash solution volumes commonlyemployed in conventional machine dishwashing methods.

Packaging for the Compositions

Commercially marketed executions of the bleaching compositions can bepackaged in any suitable container including those constructed frompaper, cardboard, plastic materials and any suitable laminates. Apreferred packaging execution is described in European Application No.94921505.7.

Abbreviations used in Examples

In the detergent compositions, the abbreviated component identificationshave the following meanings:

    ______________________________________                                        LAS:        Sodium linear C.sub.12 alkyl benzene sulfonate                    TAS:        Sodium tallow alkyl sulfate                                       CxyAS:      Sodium C.sub.1x -C.sub.1y alkyl sulfate                           C46SAS:     Sodium C.sub.14 -C.sub.16 secondary (2,3) alkyl sulfate           CxyEzS:     Sodium C.sub.1x -C.sub.ly alkyl sulfate condensed with z                      moles of ethylene oxide                                           CxyEz:      C.sub.1x -C.sub.1y predominantly linear primary alcohol                       condensed with an average of z moles of ethylene                              oxide                                                             QAS 1:      R.sub.2.N.sup.+ (CH.sub.3).sub.2 (C.sub.2 H.sub.4 OH) with                    R.sub.2 = C.sub.9 -C.sub.11 linear                                            alkyl                                                             QAS 2:      R.sub.2.N.sup.+ (CH.sub.3).sub.2 (C.sub.2 H.sub.4 OH) with                    approximately                                                                 50% R.sub.2 = C.sub.8 linear alkyl; approximately                             50% R.sub.2 = C.sub.10                                            QAS 3:      R.sub.2.N.sup.+ (CH.sub.3).sub.2 (C.sub.2 H.sub.4 OH) with                    approximately                                                                 40% R.sub.2 = C.sub.11 linear alkyl; approximately                            60% R.sub.2 = C.sub.9 linear alkyl                                QAS 4:      R.sub.2.N.sup.+ (CH.sub.3).sub.2 (C.sub.2 H.sub.4 OH) with                    R.sub.2 = C.sub.6 linear alkyl                                    QAS 5:      R.sub.2.N.sup.+ (CH.sub.3).sub.2 (C.sub.2 H.sub.4 OH) with                    R.sub.2 = C.sub.10 linear                                                     alkyl                                                             APA:        Aliphatic polyamine Indosol E-50 (Sandoz)                         DMDAA:      Dimethyldiallyl ammonium chloride (Croscolor                                  NOH) (Crosfield)                                                  Soap:       Sodium linear alkyl carboxylate derived from an                               80/20 mixture of tallow and coconut oils                          CFAA:       C.sub.12 -C.sub.14 (coco) alkyl N-methyl glucamide                TFAA:       C.sub.16 -C.sub.18 alkyl N-methyl glucamide                       TPKFA:      C.sub.12 -C.sub.14 topped whole cut fatty acids                   STPP:       Anhydrous sodium tripolyphosphate                                 TSPP:       Tetrasodium pyrophosphate                                         Zeolite A:  Hydrated Sodium Aluminosilicate of formula                                    Na.sub.12 (AlO.sub.2 SiO.sub.2).sub.12.27H.sub.2 O having a                   primary                                                                       particle size in the range from 0.1 to 10                                     micrometers                                                       Zeolite MAP:                                                                              Hydrated sodium aluminosilicate zeolite MAP                                   having a silicon to aluminium ratio of 1.07                       NaSKS-6:    Crystalline layered silicate of formula δ-                              Na.sub.2 Si.sub.2 O.sub.5                                         Citric acid:                                                                              Anhydrous citric acid                                             Borate:     Sodium borate                                                     Carbonate:  Anydrous sodium carbonate with a particle size                                between 200 μm and 900 μm                                   Bicarbonate:                                                                              Anhydrous sodium bicarbonate with a particle                                  size distribution between 400 μm and 1200 μm                Silicate:   Amorphous Sodium Silicate (SiO.sub.2 :Na.sub.2 O = 2.0:1)         Sodium sulfate:                                                                           Anhydrous sodium sulfate                                          Citrate:    Tri-sodium citrate dihydrate of activity 86.4%                                with a particle size distribution between 425 μm                           and 850 μm                                                     MA/AA:      Copolymer of 1:4 maleic/acrylic acid, average                                 molecular weight about 70,000                                     AA:         Sodium polyacrylate polymer of average                                        molecular weight 4,500                                            CMC:        Sodium carboxymethyl cellulose                                    Cellulose ether:                                                                          Methyl cellulose ether with a degree of                                       polymerization of 650 available from Shin Etsu                                Chemicals                                                         Protease:   Proteolytic enzyme of activity 4 KNPU/g sold by                               NOVO Industries A/S under the tradename                                       Savinase                                                          Alcalase:   Proteolytic enzyme of activity 3 AU/g soId by                                 NOVO Industries A/S                                               Cellulase:  Cellulytic enzyme of activity 1000 CEVU/g sold                                by NOVO Industries A/S under the tradename                                    Carezyme                                                          Amylase:    Amylolytic enzyme of activity 120 KNU/g sold                                  by NOVO Industries A/S under the tradename                                    Termamyl 120T                                                     Lipase:     Lipolytic enzyme of activity 100 KLU/g sold                                   by NOVO Industries A/S under the tradename                                    Lipolase                                                          Endolase:   Endoglucanase enzyme of activity 3000 CEVU/g                                  sold by NOVO Industries A/S                                       PB4:        Sodium perborate tetrahydrate of nominal                                      formula NaBO.sub.2.3H.sub.2 O.H.sub.2 O.sub.2                     PB1:        Anhydrous sodium perborate bleach of nominal                                  formula NaBO.sub.2.H.sub.2 O.sub.2                                Percarbonate:                                                                             Sodium percarbonate of nominal formula                                        2Na.sub.2 CO.sub.3.3H.sub.2 O.sub.2                               NOBS:       Nonanoyloxybenzene sulfonate in the form of the                               sodium salt                                                       TAED:       Tetraacetylethylenediamine                                        Mn catalyst:                                                                              Mn.sup.IV .sub.2 (m-O).sub.3 (1,4,7-trimethyl-1,4,7-                          triazacyclononane).sub.2 (PF.sub.6).sub.2, as described in                    U.S.                                                                          Pat. Nos. 5,246,621 and 5,244,594.                                DTPA:       Diethylene triamine pentaacetic acid                              DTPMP:      Diethylene triamine penta (methylene                                          phosphonate), marketed by Monsanto under the                                  Tradename Dequest 2060                                            Photoactivated bleach:                                                                    Sulfonated Zinc Phthlocyanine encapsulated in                                 bleach dextrin soluble polymer                                    Brightener 1:                                                                             Disodium 4,4'-bis(2-sulphostyry)biphenyl                          Brightener 2:                                                                             Disodium 4,4'-bis(4-anilino-6-morpholino-1.3.5-                               triazin-2-yl)amino) stilbene-2:2'-disulfonate                     HEDP:       1,1-hydroxyethane diphosphonic acid                               EDDS:       Ethylenediamine-N,N-disuccinic acid                               QEA:        bis((C.sub.2 H.sub.5 O)(C.sub.2 H.sub.4 O.sub.n)(CH.sub.3)-N.s                up.+ -C.sub.6 H.sub.12 -N.sup.+ -                                             (CH.sub.3) bis((C.sub.2 H.sub.5 O)--(C.sub.2 H.sub.4 O).sub.n)                , wherein                                                                     n = 20-30                                                         PEGX:       Polyethylene glycol, with a molecular weight of x                 PEO:        Polyethylene oxide, with a molecular weight of                                50,000                                                            TEPAE:      Tetraethylenepentaamine ethoxylate                                PVP:        Polyvinylpyrolidone polymer                                       PVNO:       Polyvinylpyridine N-oxide                                         PVPVI:      Copolymer of polyvinylpyrolidone and                                          vinylimidazole                                                    SRP 1:      Sulfobenzoyl and capped esters with oxyethylene                               oxy and terephtaloyl backbone                                     SRP 2       Diethoxylated poly (1,2 propylene terephtalate)                               short block polymer                                               Silicone antifoam:                                                                        Polydimethylsiloxane foam controller with                                     siloxane-oxyalkylene copolymer as dispersing                                  agent in a ratio of 10:1 to 100:1                                 Wax:        Paraffin wax                                                      ______________________________________                                    

In the following examples all levels are quoted as % by weight of thecomposition:

EXAMPLE 1

The following high density granular laundry detergent compositions A toF of particular utility under European machine wash conditions areexamples of the present invention:

    ______________________________________                                                   A       B       C    D     E    F                                  ______________________________________                                        LAS        8.0     8.0     8.0  --    8.0  --                                 C25E3      7.4     3.4     3.4  10.4  3.4  15.9                               C46AS      --      2.0     2.5  --    3.0  --                                 C68AS      --      2.0     5.0  7.0   1.0  --                                 QAS 1      0.05    --      --   --    --   0.8                                QAS 2      --      0.05    0.8  --    --   --                                 QAS 3      --      --      --   1.4   1.0  --                                 APA        0.5     1.0     --   --    --   2.0                                DMDAA      --      --      0.5  0.5   1.5  --                                 Zeolite A  18.1    18.1    16.1 18.1  18.1 18.1                               Zeolite MAP                                                                              --      4.0     3.5  --    --   --                                 Carbonate  12.0    12.0    13.0 26.0  26.0 26.0                               Silicate   1.4     1.4     1.4  3.0   3.0  3.0                                NaSKS-6(citric                                                                           11.0    6.0     6.0  --    --   12.5                               acid 79:21)                                                                   Sodium Sulfate                                                                           26.1    26.1    25.0 16.1  22.5 7.1                                MA/AA      0.3     0.3     0.3  0.3   0.3  0.3                                CMC        0.2     0.2     0.2  0.2   0.2  0.2                                PB4        9.0     9.0     9.0  9.0   9.0  9.0                                TAED       1.5     1.5     1.0  1.5   --   1.5                                Mn Catalyst                                                                              --      0.03    0.07 --    --   --                                 DTPMP      0.25    0.25    --   0.25  0.25 0.25                               HEDP       0.3     0.3     0.2  0.2   0.3  0.3                                EDDS       --      --      0.4  0.2   --   --                                 QEA        1.0     0.8     0.7  1.2   --   0.5                                Protease   0.85    0.85    0.26 0.85  0.85 0.85                               Amylase    0.1     0.1     0.4  0.3   0.1  0.1                                Lipase     0.05    0.6     0.7  0.1   0.07 0.1                                Photoactivated                                                                           15 ppm  15 pp   15 pp                                                                              15 pp 15 pp                                                                              15 pp                              bleach (ppm)                                                                  Brightener 1                                                                             0.09    0.09    --   0.09  0.09 0.09                               Perfume    0.3     0.3     0.3  0.3   0.3  0.3                                Silicone   0.5     0.5     0.5  0.5   0.5  0.5                                antifoam                                                                      Misc(minors to                                                                100%                                                                          Density in g/liter                                                                       850     850     850  850   850  850                                ______________________________________                                    

EXAMPLE 2

The following granular laundry detergent compositions G to I ofparticular utility under European machine wash conditions are examplesof the present invention:

    ______________________________________                                                        G         H       I                                           ______________________________________                                        LAS             --        --      4.76                                        TAS             --        --      1.57                                        C45AS           --        --      3.89                                        C25E3S          --        10.47   1.18                                        C45E7           3.3       --      5.0                                         C25E3           6.6       5.5     --                                          QAS 1           0.8       3.0     2.5                                         APA             0.5       --      --                                          DMDAA           --        1.0     1.0                                         STPP            19.7      --      --                                          Zeolite A       --        19.5    19.5                                        Zeolite MAP     2.0       --      --                                          NaSKS-6/citric acid(79:21)                                                                    --        13.0    10.6                                        Carbonate       5.1       17.4    21.4                                        Bicarbonate     --        2.0     2.0                                         Silicate        6.8       --      --                                          Sodium Sulfate  37.0      --      6.0                                         MA/AA           0.8       1.6     1.6                                         CMC             0.2       0.4     0.4                                         PB4             5.0       12.7    --                                          Percarbonate    5.0       --      12.7                                        TAED            0.5       3.1     --                                          Mn Catalyst     0.04      --      --                                          DTPMP           0.25      0.2     0.2                                         HEDP            --        0.3     0.3                                         QEA             0.9       --      --                                          Protease        0.85      2.8     0.85                                        Lipase          0.15      0.25    0.15                                        Cellulase       0.28      0.28    0.28                                        Amylase         0.4       0.1     0.1                                         PVP             0.9       1.3     0.8                                         Photoactivated bleach                                                                         15 ppm    27 ppm  27 ppm                                      (ppm)                                                                         Brightener 1    0.08      0.19    0.19                                        Brightener 2    --        0.04    0.04                                        Perfume         0.3       0.3     0.3                                         Silicone antifoam                                                                             0.5       2.4     2.4                                         Minors/misc to 100%                                                                           1.3       1.1     0.3                                         ______________________________________                                    

EXAMPLE 3

The following detergent formulations of particular utility underEuropean machine wash conditions are examples of the present invention.

    ______________________________________                                                       J      K         L    M                                        ______________________________________                                        Blown powder                                                                  LAS            6.0    5.0       11.0 6.0                                      TAS            2.0    --         --  2.0                                      QAS 2          0.8    1.0       --   --                                       QAS 3          --     --        1.5  0.6                                      APA            0.5    --        0.2  1.0                                      DMPAA          --     0.5       0.3  --                                       Zeolite A      --     27.0      --   20.0                                     STPP           24.0   --        24.0 --                                       Sulfate        6.0    6.0       9.0  --                                       MA/AA          2.0    4.0       6.0  4.0                                      Silicate       7.0    3.0       3.0  3.0                                      CMC            1.0    1.0       0.5  0.6                                      QEA            --     --        1.4  0.5                                      Brightener     0.2    0.2       0.2  0.2                                      Silicone antifoam                                                                            1.0    1.0       1.0  0.3                                      DTPMP          0.4    0.4       0.2  0.4                                      Spray on                                                                      C45E7          --     --        --   5.0                                      C45E5          2.5    2.5       2.0  --                                       C45E3          2.6    2.5       2.0  --                                       Perfume        0.3    0.3       0.3  0.2                                      Silicone antifoam                                                                            0.3    0.3       0.3  --                                       Dry additives                                                                 Sulfate        2.5    2.5       4.5  9.0                                      Carbonate      6.0    13.0      15.0 11.0                                     PB1            --     --        --   1.5                                      PB4            18.0   18.0      10.0 18.5                                     TAED           3.0    2.0       --   2.0                                      EDDS           --     2.0       2.4  --                                       Protease       3.25   1.0       3.25 3.25                                     Lipase         0.4    0.5       0.4  0.2                                      Amylase        0.2    0.2       0.2  0.4                                      Photoactivated bleach                                                                        --     --        --   0.15                                     Minors/misc to 100%                                                           ______________________________________                                    

EXAMPLE 4

The following granular detergent formulations are examples of thepresent invention. Formulation N is particularly suitable for usageunder Japanese machine wash conditions. Formulations O to S areparticularly suitable for use under US machine wash conditions.

    ______________________________________                                                     N      O      P    Q     R    S                                  ______________________________________                                        Blown powder                                                                  LAS          22.0   5.0    4.0  9.0   8.0  7.0                                C45AS        7.0    7.0    6.0  --    --   --                                 C46AS        --     4.0    3.0  --    --   --                                 C45E35       --     3.0    2.0  8.0   5.0  4.0                                QAS 1        0.5    --     --   --    --   --                                 QAS 2        --     0.5    --   2.0   --   3.5                                QAS 3        --     --     0.8  --    3.0  --                                 APA          0.5    0.5    0.5  --    --   --                                 DMPAA        --     --     --   0.5   0.5  0.5                                Zeolite A    6.0    16.0   14.0 19.0  16.0 14.0                               MA/AA        6.0    3.0    3.0  --    --   --                                 AA           --     3.0    3.0  2.0   3.0  3.0                                Sodium Sulfate                                                                             5.5    2.5    1.8  23.0  12.5 18.5                               Silicate     5.0    1.0    1.0  2.0   1.0  1.0                                Carbonate    28.3   9.0    3.0  25.7  8.0  6.0                                QEA          0.4    0.4    --   --    0.5  1.1                                PEG 4000     0.5    --     1.5  1.0   1.5  1.0                                Sodium oleate                                                                              2.0    --     --   --    --   --                                 DTPA         0.4    --     0.5  --    --   0.5                                Brightener   0.2    0.3    0.3  0.3   0.3  0.3                                Spray on                                                                      C25E5        1.0    --     --   --    --   --                                 C45E7        --     2.0    2.0  0.5   2.0  2.0                                Perfume      1.0    0.3    0.3  1.0   0.3  0.3                                Agglomerates                                                                  C45AS        --     5.0    5.0  --    5.0  5.0                                LAS          --     2.0    2.0  --    2.0  2.0                                Zeolite A    --     7.5    7.5  --    7.5  7.5                                HEDP         --     1.0    --   --    2.0  --                                 Carbonate    --     4.0    4.0  --    4.0  4.0                                PEG 4000     --     0.5    0.5  --    0.5  0.5                                Misc(water etc)                                                                            --     2.0    2.0  --    2.0  2.0                                Dry additives                                                                 TAED         1.0    2.0    3.0  1.0   3.0  2.0                                PB4          --     1.0    4.0  --    5.0  0.5                                PB1          6.0    --     --   --    --   --                                 Percarbonate --     5.0    12.5 --    --   --                                 Carbonate    --     5.3    0.8  --    2.5  4.0                                NOBS         4.5    --     6.0  --    --   0.6                                Cumeme sulfonic acid                                                                       --     2.0    2.0  --    2.0  2.0                                Lipase       1.6    0.4    0.4  0.1    0.05                                                                              0.2                                Cellulase    --     0.2    0.2  --    0.2  0.2                                Amylase      --     0.3    0.3  --    --   --                                 Protease     --     1.6    1.6  --    1.6  1.6                                PVPVI        --     0.5    --   --    --   --                                 PVP          0.5    --     --   --    --   --                                 PVNO         --     0.5    0.5  --    --   --                                 SRP1         --     0.5    0.5  --    --   --                                 Silicone antifoam                                                                          --     0.2    0.2  --    0.2  0.2                                Minors/misc to 100%                                                           ______________________________________                                    

EXAMPLE 5

The following granular detergent formulations are examples of thepresent invention. Formulations W and X are of particular utility underUS machine wash conditions. Y is of particular utility under Japanesemachine wash conditions

    ______________________________________                                                         T          U      V                                          ______________________________________                                        Blown Powder                                                                  Zeolite A        30.0       22.0   6.0                                        Sodium Sulfate   18.0       5.0    7.0                                        MA/AA            3.0        2.0    6.0                                        LAS              14.0       12.0   22.0                                       C45AS            8.0        7.0    7.0                                        QAS 1            0.7        --      --                                        QAS 2            --         2.2    --                                         QAS 5            --         --     1.5                                        APA              1.0        1.0    1.5                                        Silicate         --         1.0    5.0                                        Soap             --         --     2.0                                        Brightener 1     0.2        0.2    0.2                                        Carbonate        7.0        15.0   18.5                                       DTPMP            --         0.4    0.4                                        Spray On         --         1.0    5.0                                        C45E7            1.0        1.0    1.0                                        Dry additives                                                                 HEDP             1.0        --     --                                         PVPVI/PVNO       0.5        0.5    0.5                                        Protease         3.225      3.25   3.25                                       Lipase           0.4        0.1    0.2                                        Amylase          0.1        0.1    0.1                                        Cellulase        0.1        0.1    0.1                                        TAED             --         6.1    4.5                                        PB1              11.0       5.0    6.0                                        Sodium Sulfate   --         6.0    --                                         Balance (Moisture and Misc.)                                                  ______________________________________                                    

EXAMPLE 6

The following granular detergent compositions of particular utilityunder European wash conditions were are examples of the presentinvention.

    ______________________________________                                                            W       X                                                 ______________________________________                                        Blown powder                                                                  Zeolite A           20.0    --                                                STPP                --      20.0                                              LAS                 6.0     6.0                                               C68AS               2.0     2.0                                               QAS 1               0.01    --                                                QAS 4               --      0.6                                               DMDAA               5.5     0.5                                               Silicate            3.0     8.0                                               MA/AA               4.0     2.0                                               CMC                 0.6     0.6                                               Brightener 1        0.2     0.2                                               DTPMP               0.4     0.4                                               Spray on                                                                      C45E7               5.0     5.0                                               Silicone antifoam   0.3     0.3                                               Perfume             0.2     0.2                                               Dry additives                                                                 Carbonate           14.0    9.0                                               PB1                 1.5     2.0                                               PB4                 18.5    13.0                                              TAED                2.0     2.0                                               Photoactivated bleach                                                                             15 ppm  15 ppm                                            Protease            1.0     1.0                                               Lipase              0.2     0.08                                              Amylase             0.4     0.4                                               Cellulase           0.1     0.1                                               Sulfate             9.5     19.5                                              Balance (Moisture and Misc.)                                                                      10.6    5.12                                              Density (g/liter)   700     700                                               ______________________________________                                    

EXAMPLE 7

The following detergent compositions are examples of the presentinvention:

    ______________________________________                                                          Y        Z       AA                                         ______________________________________                                        Blown Powder                                                                  Zeolite A         15.0     15.0    15.0                                       Sodium Sulfate    0.0      0.0     0.0                                        LAS               3.0      3.0     3.0                                        QAS 2             1.0      --       --                                        QAS 5             --       3.0     2.0                                        APA               0.5      0.5     0.5                                        DTPMP             0.4      0.2     0.4                                        CMC               0.4      0.4     0.4                                        MA/AA             4.0      2.0     2.0                                        Agglomerates                                                                  LAS               5.0      5.0     5.0                                        TAS               2.0      2.0     1.0                                        Silicate          3.0      3.0     4.0                                        QEA               --       1.0     0.6                                        Mn Catalyst       0.03     --      --                                         Zeolite A         8.0      8.0     8.0                                        Carbonate         8.0      8.0     4.0                                        Spray On                                                                      Perfume           0.3      0.3     0.3                                        C45E7             2.0      2.0     2.0                                        C25E3             2.0      --      --                                         Dry additives                                                                 Citrate           5.0      --      2.0                                        Bicarbonate       --       3.0     --                                         Carbonate         8.0      12.0    5.0                                        Percarbonate      --       7.0     10.0                                       TAED              6.0      2.0     5.0                                        PB1               14.0     7.0     8.0                                        EDDS              --       2.0     --                                         Polyethylene oxide of MW 5,000,000                                                              --       --      0.2                                        Bentonite clay    --       --      10.0                                       Protease          1.0      3.25    3.25                                       Lipase            0.4      0.1     1.0                                        Amylase           0.6      0.6     --                                         Cellulase         0.6      0.6     --                                         Silicone antifoam 5.0      5.0     5.0                                        Dry additives                                                                 Sodium sulfate    0.0      3.0     0.0                                        Balance (Moisture and Misc.) to                                               100%                                                                          Density (g/liter) 850      850     850                                        ______________________________________                                    

EXAMPLE 8

The following detergent formulations are examples of the presentinvention:

    ______________________________________                                                      BB      CC        DD   EE                                       ______________________________________                                        LAS           20.0    14.0      24.0 22.0                                     QAS 1         0.7     1.0       0    0                                        QAS 2         --       --       0.08 --                                       QAS 4         --      --        --   1.0                                      TFAA          --      1.0       --   --                                       C25E5/C45E7   --      2.0       --   0.5                                      C45E3S        --      2.5       --   --                                       STPP          30.0    18.0      30.0 22.0                                     Silicate      9.0     5.0       10.0 8.0                                      Carbonate     13.0    7.5       --   5.0                                      Bicarbonate   --      7.5       --   --                                       Percarbonate  --      5.0       9.0  15.0                                     DTPMP         0.7     1.0       --   --                                       QEA 1         0.4     1.2       0.5  2.0                                      QEA 2         0.4     --        --   --                                       DMDAA         1.0     0.5       2.0  1.0                                      SRP 1         0.3     0.2       --   0.1                                      MA/AA         2.0     1.5       2.0  1.0                                      CMC           0.8     0.4       0.4  0.2                                      Protease      2.6     3.25      1.6  1.6                                      Amylase       0.8     0.4       --   --                                       Lipase        0.2     0.06      0.25 0.1                                      Cellulase     0.15    0.05      --   --                                       Photoactivated                                                                              70 ppm  45 ppm    --   10 ppm                                   bleach (ppm)                                                                  Brightener 1  0.2     0.2       0.08 0.2                                      PB 1          6.0     2.0       --   --                                       HEDP          --      --        2.3  --                                       TAED          2.0     1.0       --   --                                       Balance (Moisture                                                             and Misc.) to 100%                                                            ______________________________________                                    

What is claimed is:
 1. A detergent composition comprising:(a) from 0.25%to 3%, by weight of composition of at least one cation surfactant of theformula:

    R.sup.1 R.sup.2 R.sup.3 R.sup.4 N.sup.+ X.sup.-            (I)

wherein R¹ is an optionally substituted phenol or hydroxyalkyl grouphaving no greater than 6 carbon atoms; each of R² and R³ isindependently selected from C₁₋₄ alkyl or alkenyl; R⁴ is a C₅₋₁₁ alkylor alkenyl; and X is a counter ion; (b) from 1% to 50%, by weight ofcomposition of at least one anionic surfactant; (c) optionally, from0.5% to 20%, by weight of composition of at least one nonionicsurfactant; (d) from 0.01% to 50%, by weight of composition of acationic dye-fixing agent; (e) from about 0.01% to 10% by weight ofcomposition of polymeric dye transfer inhibiting agent; (f) from about1% to about 40%. by weight of composition of a source of hydrogenperoxide selected from the group consisting of perborate, percarbonate,perphosphate, persulfate, persilicate and mixtures thereof; and (g) atransition metal bleach catalyst;wherein the weight ratio of saidcationic dye-fixing agent to said cationic surfactant is from 50:1 to1:10.
 2. A detergent composition according to claim 1 wherein saidcomposition comprises a nonionic surfactant selected from the groupconsisting of alkylalkoxylates, polyhydroxy fatty acid amides, fattyacid amides, alcohol ethoxylates, alkyl phenol ethoxylates,alkylpolysaccharides, alkyl alkoxylated sulfates; and mixtures thereof.3. A detergent composition according to claim 1 wherein said anionicsurfactant comprises a mixture of:(i) from 3% to about 40%, by weight ofthe composition, of at least one alkyl sulfate surfactant of the formulaR⁵ OSO₃ M; and (ii) from 6% to about 23%, by weight of the composition,of an alkyl benzene sulfonate of the formula R⁶ SO₃ M; wherein R⁵ isC₉₋₂₂ alkyl; R⁶ is C₁₀₋₂₀ alkyl benzene; and M is alkali metals,alkaline earth metals, alkanolammonium, ammonium and mixtures thereof.4. A detergent composition according to claim 1 wherein said compositioncomprises more than one of said cationic surfactants and wherein furtherat least 10% of said cationic surfactants have R⁴ which is C₅₋₉ alkyl oralkenyl.
 5. A detergent composition according to claim 1 wherein R1 isselected from the group consisting of --CH₂ CH₂ OH, --CH₂ CH₂ CH₂ OH,--CH₂ CH(CH₃)OH, and CH(CH₃)CH₂ OH.
 6. A detergent composition accordingto claim 1 wherein said composition further comprises one or moreselected from the group consisting of organic polymeric compounds,enzymes, suds suppressors, lime soap dispersants, soil releasing agents,corrosion inhibitors and mixtures thereof.
 7. A detergent compositionaccording to claim 1 wherein said composition further comprises a fabricsoftening compound.
 8. A detergent composition according to claim 1wherein said cationic dye-fixing agent is selected from the groupconsisting of dimethyldiallyl ammonium chloride,oleylmethyldiethylenediaminemethsulfate, mono stearyl-ethylenediaminotrimethylammonium methosulfate, polyamine-cyanuric chloridecondensates, aminated glycerol dichlorohydrine and mixtures thereof. 9.A detergent composition according to claim 1 wherein said transitionmetal catalyst is selected from the group consisting of cobaltcatalysts, manganese catalysts, iron catalysts, copper catalysts andmixtures thereof.
 10. A washing or rinsing method for laundry in adomestic washing machine in which a dispensing device containing aneffective amount of a detergent composition according to claim 6 isintroduced into the washing machine before the commencement of the wash,wherein said dispensing device permits progressive release of saiddetergent composition into the wash liquor during the wash.